JP2019526439A - Synthesis and characterization of metathesis catalysts - Google Patents

Abstract

The present invention generally relates to olefin metathesis catalysts, the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the synthesis of olefin metathesis and related olefin metathesis catalysts. The use of such compounds. The present invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial applications such as oil and gas, fine chemicals and pharmaceuticals (FIG. 1).

Description

(Related application)
This application claims the benefit of US Provisional Patent Application No. 62 / 378,791, filed Aug. 24, 2016.

  The present invention generally relates to olefin metathesis catalysts, the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the synthesis of olefin metathesis and related olefin metathesis catalysts. The use of such compounds. The present invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial applications such as oil and gas, fine chemicals and pharmaceuticals.

  Since the discovery in the 1950s, olefin metathesis has emerged as a valuable synthesis method for producing carbon-carbon double bonds. Recent advances in organic and polymer synthesis applications are largely dependent on the development of well-defined olefin metathesis catalysts.

  The ruthenium metathesis catalyst technology has allowed the development of several research platforms such as ring-opening metathesis polymerization (ROMP), ring-opening cross-metathesis (ROCM), cross-metathesis (CM) and ring-closing metathesis (RCM).

First generation Grubbs ruthenium olefin metathesis catalyst, eg
(PCy ₃ ) ₂ (Cl) ₂ Ru═CHPh has been widely used in organic synthesis.

The incorporation of certain types of N-heterocyclic carbene (NHC) ligands plays an important role in the development of ruthenium metathesis catalysts, such as second generation Grubbs ruthenium olefin metathesis catalysts such as
_{(IMesH 2) (PCy 3)} (Cl) 2 Ru = CHPh is obtained, wherein, IMesH ₂ is 1,3-dimesityl-4,5-dihydro-2-ylidene.

In order to exchange phosphines with second generation Grubbs ruthenium olefin metathesis catalysts, the Grubbs group in 2001, a precursor with two pyridine ligands (IMesH ₂ ) (Cl) ₂ (C ₅ H ₅ N) A method involving ₂ Ru = CHPh has been reported (Organometallics 2001, 20, 5314-5318). This unstable pyridine ligand enabled the preparation of various ruthenium olefin metathesis catalysts. However, the preparation of pyridine complexes requires a large amount of expensive and offensive reagent (pyridine) and various reaction conditions (minus Celsius), especially for industrial scale-up.

Organometallics 2001, 20, 5314-5318

  Therefore, there is always a need for efficient, high yield, high purity and easy in scale-up procedures to synthesize olefin metathesis catalysts, especially second generation Grubbs ruthenium olefin metathesis catalysts. .

  In order to meet this need, the inventors have developed a novel ruthenium olefin metathesis catalyst having a sulfoxide ligand as described herein. The ruthenium olefin metathesis catalyst with this labile sulfoxide ligand is highly stable and has a variety of second generation Grubbs ruthenium olefin metathesis in higher yields and purity compared to existing procedures. Facilitates catalyst synthesis.

式中、
Ｍは、第８族遷移金属であり；一般には、Ｍは、ルテニウムまたはオスミウムであり；典型的には、Ｍは、ルテニウムであり；
Ｌ^１およびＬ^２は、独立して、中性の電子供与配位子であり；
ｎは、０または１であり；典型的には、ｎは０であり；
ｍは、０、１または２であり；典型的には、ｍは０であり；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｂは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；または、Ｒ^ａとＲ^ｂが一緒に結合して、スルホキシド基［−Ｓ（Ｏ）−］を有する５員環または６員環のヘテロ環式環を形成し；
Ｘ^１およびＸ^２は、独立してアニオン性配位子であり；一般には、Ｘ^１およびＸ^２は、独立して、ハロゲン、トリフルオロアセテート、ペルフルオロフェノレート、チオレート、アルキルチオ、アリールチオまたはニトレートであり；典型的には、Ｘ^１およびＸ^２は、独立して、Ｃｌ、Ｂｒ、ＩまたはＦであり；
Ｒ^１およびＲ^２は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであるか；典型的には、Ｒ^１は水素であり、Ｒ^２は、非置換フェニル、置換フェニルまたは置換１−プロペニルであり；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成する。 In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (I):

Where
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ¹ and L ² are independently neutral electron donor ligands;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are bonded together to form a sulfoxide group [—S (O) —] Forming a 5- or 6-membered heterocyclic ring having
X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate Typically; typically X ¹ and X ² are independently Cl, Br, I or F;
Are R ¹ and R ² independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen; ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene.

  In one embodiment, the present invention provides a method of synthesizing the olefin metathesis catalyst of the present invention.

  In one embodiment, the present invention provides a method of using the olefin metathesis catalyst of the present invention in a metathesis reaction.

  In one embodiment, the present invention provides a method of synthesizing a second generation Grubbs catalyst generation using the olefin metathesis catalyst of the present invention.

  Other embodiments of the invention are described herein.

  These and other aspects of the invention will be apparent to those skilled in the art in light of the following detailed description and examples. Furthermore, it is to be understood that any embodiment or example of the invention described herein should not be construed as limiting.

FIG. 1 shows the C747 Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram. FIG. 2 shows a C647 _m Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram. FIG. 3 shows the conversion of diethyl 2,2-diallyl malonate to 4,4-bis (ethoxycarbonyl) cyclo-pentene in the presence of a series of ruthenium catalysts.

  Unless otherwise indicated, the present invention is not limited to specific reagents, substituents, catalysts, reaction conditions, and the like. This is because they can vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and should not be construed as limiting.

  As used in this specification and the appended claims, the singular forms “a”, “an” and “the” are clearly different in their contents. A plurality of objects are also included unless otherwise indicated. Thus, for example, reference to “an olefin” includes one olefin and a combination or mixture of two or more olefins, and reference to “a substituent” Includes one substituent and two or more substituents.

  As used herein and in the appended claims, "for example", "for instance", "such as" or "including" The terminology is intended to introduce examples to further clarify the more comprehensive specifics. Unless otherwise specified, these examples are provided only to assist in understanding the present invention and are not intended to be limiting in any way.

  In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings:

  The term “alkyl” as used herein is a straight, branched or cyclic saturated hydrocarbon group, typically but not necessarily, 1 to 30 carbon atoms. Including 1 to 24 carbon atoms, typically including 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n- Refers to butyl, iso-butyl, t-butyl, octyl, decyl, and the like, and cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. The term “lower alkyl” intends an alkyl group containing 1 to 6 carbon atoms, the specific term “cycloalkyl” is a cyclic alkyl group, typically 4-8, Preferably those containing 5 to 7 carbon atoms are intended. The term “substituted alkyl” refers to an alkyl substituted with one or more substituents, and the terms “heteroatom-containing alkyl” and “heteroalkyl” replace at least one carbon atom with a heteroatom. Refers to alkyl. Unless otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted and / or heteroatom-containing alkyl and lower alkyl, respectively.

  The term “alkylene” as used herein refers to a divalent linear, branched or cyclic alkyl group, where “alkyl” is as defined herein.

  The term “alkenyl” as used herein refers to a straight, branched or cyclic hydrocarbon group containing from 2 to 30 carbon atoms and containing at least one double bond, for example Ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracocenyl and the like. In general, an “alkenyl” group herein contains 2 to 24 carbon atoms, and typically an “alkenyl” group herein contains 2 to 12 carbon atoms. The term “lower alkenyl” intends an “alkenyl” group containing 2 to 6 carbon atoms, a specific term “cycloalkenyl” refers to a cyclic “alkenyl” group, typically 5 Intended to contain ˜8 carbon atoms. The term “substituted alkenyl” refers to “alkenyl” substituted with one or more substituents, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to at least one carbon atom being a heteroatom. Refers to “alkenyl” replaced by Unless otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted and / or heteroatom-containing “alkenyl” and lower “alkenyl”, respectively. The term “alkenyl” is used interchangeably with the term “olefin” herein.

  The term “alkenylene” as used herein refers to a divalent straight chain, branched chain or cyclic alkenyl group, where “alkenyl” is as defined herein.

  The term “alkynyl” as used herein refers to a straight or branched chain hydrocarbon group containing at least one triple bond and containing 2 to 30 carbon atoms, such as ethynyl, It refers to n-propynyl and the like. Generally, an “alkynyl” group herein contains 2 to 24 carbon atoms. Typical “alkynyl” groups contain 2 to 12 carbon atoms. The term “lower alkynyl” intends an “alkynyl” group containing 2 to 6 carbon atoms. The term “substituted alkynyl” refers to “alkynyl” substituted with one or more substituents, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” are those in which at least one carbon atom is a heteroatom. Refers to “alkynyl”. Unless otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing “alkynyl” and lower “alkynyl”, respectively.

  The term “alkoxy” as used herein refers to an alkyl group attached through one terminal ether linkage. That is, an “alkoxy” group can be represented as —O-alkyl, where alkyl is as defined herein. A “lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, “alkenyloxy” and “lower alkenyloxy” refer to an alkenyl group and a lower alkenyl group bonded through one terminal ether bond, respectively, and “alkynyloxy” and “lower alkynyloxy” An alkynyl group and a lower alkynyl group bonded through one terminal ether bond.

  The term “aryl”, as used herein, unless otherwise specified, contains one aromatic ring, or is directly attached or indirectly attached (different). Aromatic substituents comprising a plurality of fused aromatic rings, such that the aromatic ring is attached to a common group such as a methylene moiety or an ethylene moiety. “Aryl” groups contain 5 to 30 carbon atoms, generally “aryl” groups contain 5 to 20 carbon atoms, and typically “aryl” groups contain 5 to 14 carbon atoms. Of carbon atoms. Exemplary “aryl” groups include one aromatic ring or two fused or bonded aromatic rings, including, for example, phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituents, such as 2,4,6-trimethylphenyl (ie, mesityl or Mes), 2-methyl-phenyl, 2,6-di- -Iso-propylphenyl (ie, DIPP or DiPP), 2-isopropyl-phenyl (ie, IPP, Ipp or ipp), 2-iso-propyl-6-methylphenyl (ie, MIPP, Mipp or MiPP). The terms “heteroatom-containing aryl” and “heteroaryl” refer to an “aryl” substituent in which at least one carbon atom is replaced with a heteroatom, as described in further detail below.

  The term “aryloxy” as used herein refers to an aryl group attached through one terminal ether linkage, where “aryl” is as defined herein. An “aryloxy” group can be represented as —O-aryl, where aryl is as defined herein. Preferred “aryloxy” groups contain 5 to 24 carbon atoms, and particularly preferred “aryloxy” groups contain 5 to 14 carbon atoms. Examples of “aryloxy” groups include, but are not limited to, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy- Examples include phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy and the like.

  The term “alkaryl” refers to an aryl group having an alkyl substituent, the term “aralkyl” refers to an alkyl group having an aryl substituent, and “aryl” and “alkyl” are as used herein. As defined. “Alkaryl” and “aralkyl” groups contain 6 to 30 carbon atoms; in general, “alkaryl” and “aralkyl” groups contain 6 to 20 carbon atoms, typically The “alkaryl” and “aralkyl” groups contain 6 to 16 carbon atoms. Examples of the “alkaryl” group include p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4- Examples include dienes. Examples of “aralkyl” groups include, but are not limited to, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4 -Phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl and the like can be mentioned. The terms “alkaryloxy” and “aralkyloxy” refer to a substituent of the formula —OR, where R is “alkaryl” or “aralkyl”, respectively, as defined herein.

  The term “acyl” refers to a substituent having the formula — (CO) -alkyl, — (CO) -aryl or — (CO) -aralkyl, and the term “acyloxy” refers to the formula —O (CO) Refers to a substituent having -alkyl, -O (CO) -aryl or -O (CO) -aralkyl, where "alkyl", "aryl" and "aralkyl" are as defined herein.

  The terms “cyclic” and “ring” refer to alicyclic or aromatic groups, which may be substituted or unsubstituted and / or contain heteroatoms. It may not be contained and may be monocyclic, bicyclic or polycyclic. The term “alicyclic” is used in the conventional sense to refer to an alicyclic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.

  The terms “halo”, “halogen” and “halide” are used in the usual sense to refer to a chloro, bromo, fluoro or iodo substituent.

  The term “hydrocarbyl” includes monovalent “hydrocarbyl” containing 1 to 30 carbon atoms, typically containing 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms. "Moiety, including linear, branched, cyclic, saturated and unsaturated species such as alkyl, alkenyl, aryl groups and the like. The term “lower hydrocarbyl” intends a “hydrocarbyl” group containing 1 to 6 carbon atoms, typically 1 to 4 carbon atoms, and the term “hydrocarbylene” Contemplated are divalent “hydrocarbyl” moieties containing ˜30 carbon atoms, typically 1-24 carbon atoms, especially 1-12 carbon atoms, straight, branched, cyclic , Including saturated and unsaturated species. The term “lower hydrocarbylene” intends a “hydrocarbylene” group containing 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to “hydrocarbyl” substituted with one or more substituents, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” have at least one carbon atom replaced with a heteroatom. Refers to hydrocarbyl. Similarly, “substituted hydrocarbylene” refers to “hydrocarbylene” substituted with one or more substituents, and the terms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene” are at least “Hydrocarbylene” in which one carbon atom is replaced by a heteroatom. Unless otherwise indicated, the terms “hydrocarbyl” and “hydrocarbylene” should be interpreted to include substituted and / or heteroatom-containing “hydrocarbyl” and “hydrocarbylene” moieties, respectively.

  The term “heteroatom-containing”, such as “heteroatom-containing hydrocarbyl group” means that one or more carbon atoms are elements other than carbon, such as nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen. , Refers to a hydrocarbon molecule or hydrocarbyl molecular fragment replaced with oxygen or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent containing a heteroatom, and the term “heterocycle” refers to a cyclic substituent containing a heteroatom, “heteroaryl” and “hetero The term “aromatic” refers to “aryl” and “aromatic” substituents, respectively, containing heteroatoms, and the like. A “heterocyclic” group or compound may be aromatic or non-aromatic, and “heterocycle” may be a single group as described herein with respect to the term “aryl”. It may be a ring, bicycle or polycycle. Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated aminoalkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, and the like.

“Substituted” such as “substituted hydrocarbyl”, “substituted alkyl”, “substituted aryl”, etc., imply carbon (in the hydrocarbyl, alkyl, aryl or other moiety, as implied in some of the above definitions. It is intended that at least one hydrogen atom bonded to an (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, but are not limited to, a functional group referred to herein as “Fn”, such as halo, hydroxyl, sulfhydryl, C ₁ -C ₂₄ alkoxy, C ₂ -C ₂₄ alkenyloxy. , _C 2 _{-C 24 alkynyloxy,} C 5 _{-C 24 aryloxy,} C 6 _{-C 24 aralkyloxy,} C 6 _{-C 24} alkaryloxy, acyl _(C 2 _{-C 24} alkylcarbonyl (-CO- alkyl) and C ₆ -C ₂₄ arylcarbonyl containing (-CO- aryl)), acyloxy (-O- _acyl, C 2 _{-C 24} alkylcarbonyloxy (-O-CO- alkyl) and _C 6 _{-C 24} arylcarbonyloxy ( -O-CO- including _{aryl)), C} 2 ~C ₂₄ alkoxy carboxyl (- (CO) -O- Al _Le), C 6 _{-C 24} aryloxy carboxyl (- (CO) -O- aryl), halo carboxyl (- (CO) -X, where X is _halo), C 2 _{-C 24} alkylcarbonyl diisocyanatohexane ( -O- (CO) -O- _alkyl), C 6 _{-C 24} aryl carboxylate diisocyanatohexane (-O- (CO) -O- aryl), carboxyl (-COOH), a carboxylate (-COO-), carbamoyl (- (CO) _-NH 2), mono- _- (C 1 _{-C 24} alkyl) -substituted carbamoyl _{(- (CO) -NH (C} 1 ~C 24 alkyl)), di _- (C 1 _{-C 24} alkyl) -substituted carbamoyl ( _{- (CO) -N (C 1} ~C 24 _alkyl) 2), mono _{- (C} 5 _{~C 24} aryl) substituted carbamoyl (- (CO) -NH- aryl), di _{- (C} 5 _{~C 24} aryl) Conversion carbamoyl _{(- (CO) -N (C} 5 ~C 24 _aryl) 2), thiocarbamoyl (- (CS) _-NH 2), mono- _{- (C} 1 _{~C 24} alkyl) -substituted thiocarbamoyl (- (CS) -NH _(C 1 _{~C 24} alkyl)), di _{- (C} 1 _{~C 24} alkyl) -substituted thiocarbamoyl _{(- (CS) -N (C} 1 ~C 24 _alkyl) 2), mono - _(C 5 -C ₂₄ aryl) substituted thiocarbamoyl (- (CS) -NH- aryl), di _- (C 5 _{-C 24} aryl) substituted thiocarbamoyl _{(- (CS) -N (C} 5 ~C 24 _aryl) 2), carbamide ( —NH— (CO) —NH ₂ ), cyano (—C≡N), cyanato (—O—C≡N), thiocyanate (—S—C≡N), formyl (— (CO) —H), thioformyl (-(CS) -H), Mino _(-NH 2), mono- _{- (C} 1 _{~C 24} alkyl) -substituted amino, di _{- (C} 1 _{~C 24} alkyl) -substituted amino, mono _{- (C} 5 _{~C 24} aryl) -substituted amino, di - (C ₅ -C ₂₄ aryl) -substituted _amino, (C 1 _{-C 24 alkyl)} (C 5 _{-C 24} aryl) -substituted _amino, (C 2 _{-C 24} alkyl) - amide (-NH- (CO) - alkyl), ( C ₆ -C ₂₄ aryl) - amide (-NH- (CO) - aryl), imino (-CR = NH, where, R represents _hydrogen, C 1 _{-C 24 alkyl,} C 5 _{-C 24} aryl, C ₆ -C _{24 alkaryl,} C 6 _{-C 24} aralkyl, _etc.), (C 2 _{-C 20} alkyl) - imino (-N (alkyl), wherein, R represents _hydrogen, C 1 _{-C 24} alkyl, C ₅ -C ₂₄ aryl, C ₆ -C ₂₄ alkaryl, C ₆ -C ₂₄ aralkyl, etc.), arylimino (—CR═N (aryl), wherein R is hydrogen, C ₁ -C ₂₀ alkyl, C ₅ -C ₂₄ Aryl, C ₆ -C ₂₄ alkaryl, C ₆ -C ₂₄ aralkyl, etc.), nitro (—NO ₂ ), nitroso (—NO), sulfo (—SO ₂ —OH), sulfonate (—SO ₂ —O) _-), (C 1 _{-C 24} alkyl) - sulfanyl (-S- alkyl; also termed _{"alkylthio"),} (C 5 _{-C 24} aryl) - sulfanyl (-S- aryl; also termed "arylthio"), ( C ₁ -C ₂₄ alkyl) - sulfinyl (- (SO) - _{alkyl), (C} 5 ~C ₂₄ aryl) - sulfinyl (- (SO) - _{aryl), (C} 1 -C ₄ alkyl) - sulphonyl (-SO ₂ - alkyl), mono _- (C 1 _{-C 24} alkyl) - aminosulfonyl _-SO 2 -N (H) alkyl), di _- (C 1 _{-C 24} alkyl) - aminosulfonyl -SO ₂ -N _{(alkyl) 2, (C} 5 _{~C 24} aryl) - sulfonyl (-SO ₂ - aryl), boryl _(-BH 2), borono (-B _(OH) 2), boronate (-B ( OR) ₂ , where R is alkyl or other hydrocarbyl), phosphono (—P (O) (OH) ₂ ), phosphonate (—P (O) (O—) ₂ ), phosphinate (—P (O) (O-)), phospho (-PO _2), and phosphino _(-PH 2); and hydrocarbyl moieties _C 1 _{-C 24} alkyl _(preferably, C 1 _{-C 12} alkyl, more preferably Is _C 1 -C _{6 alkyl),} C 2 _{-C 24} alkenyl _(preferably, C 2 _{-C 12} alkenyl, more _preferably, C 2 -C _{6 alkenyl),} C 2 _{-C 24} alkynyl (preferably, _{C 2} -C ₁₂ alkynyl, more preferably C ₂ -C ₆ alkynyl), C ₅ -C ₂₄ aryl (preferably C ₅ -C ₁₄ aryl), C ₆ -C ₂₄ alkaryl (preferably C ₆ -C ₁₆ alkaryl) and C ₆ -C ₂₄ aralkyl (preferably C ₆ -C ₁₆ aralkyl).

  By “Grubbs-Hoveyda ligand” is intended a benzylidene ligand having a chelating alkyloxy group attached to the benzene ring in the ortho position.

  The term “sulfoxide group” refers to — [S (O)] —.

  “Functionalized” such as “functionalized hydrocarbyl”, “functionalized alkyl”, “functionalized olefin”, “functionalized cyclic olefin” means hydrocarbyl, alkyl, olefin, cyclic olefin or other moiety It is contemplated that at least one hydrogen atom bonded to a carbon (or other) atom is replaced with one or more functional groups as described herein. The term “functional group” is intended to include any functional species suitable for use as described herein. In particular, as used herein, a functional group will necessarily have the ability to react or bind to the corresponding functional group on the substrate surface.

  In addition, the functional groups described above may be substituted with one or more additional substituents, or one or more hydrocarbyl moieties (as specifically listed herein) if the particular group is tolerated. Etc.) may be further substituted. Similarly, a hydrocarbyl moiety described herein may be further substituted with one or more additional substituents or with one or more hydrocarbyl moieties (such as those specifically listed herein). Good.

  “Optional” or “optionally” means that the situation described thereafter may or may not occur, so that the description includes the situation when Includes situations where no situation occurs. For example, the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present on a given atom, and thus This description includes a structure in which a non-hydrogen substituent is present and a structure in which a non-hydrogen substituent is not present.

式中、
Ｍは、第８族遷移金属であり；一般には、Ｍは、ルテニウムまたはオスミウムであり；典型的には、Ｍは、ルテニウムであり；
Ｌ^１およびＬ^２は、独立して、中性の電子供与配位子であり；
ｎは、０または１であり；典型的には、ｎは０であり；
ｍは、０、１または２であり；典型的には、ｍは０であり；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｂは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｔ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであるか；
Ｘ^１およびＸ^２は、独立してアニオン性配位子であり；一般には、Ｘ^１およびＸ^２は、独立して、ハロゲン、トリフルオロアセテート、ペルフルオロフェノレート、チオレート、アルキルチオ、アリールチオまたはニトレートであり；典型的には、Ｘ^１およびＸ^２は、独立して、Ｃｌ、Ｂｒ、ＩまたはＦであり；
Ｒ^１およびＲ^２は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；典型的には、Ｒ^１は水素であり、Ｒ^２は、非置換フェニル、置換フェニルまたは置換１−プロペニルであり；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成する。 Olefin Metathesis Catalyst In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (I):

Where
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ¹ and L ² are independently neutral electron donor ligands;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Is methyl, ethyl, n-propyl, iso-propyl, t-butyl, tert-butyl, cyclohexyl or phenyl;
X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate Typically; typically X ¹ and X ² are independently Cl, Br, I or F;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² Is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (I), wherein:
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ¹ and L ² are independently neutral electron donor ligands;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate Typically; typically X ¹ and X ² are independently Cl, Br, I or F;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² Is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene.

式中、
Ｍは、第８族遷移金属であり；一般には、Ｍは、ルテニウムまたはオスミウムであり；典型的には、Ｍは、ルテニウムであり；
Ｌ^１は、カルベンであり；
Ｌ^２は、中性の電子供与配位子であり；
ｎは、０または１であり；典型的には、ｎは０であり；
ｍは、０、１または２であり；典型的には、ｍは０であり；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^１およびＲ^２は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；典型的には、Ｒ^１は水素であり、Ｒ^２は、非置換フェニル、置換フェニルまたは置換１−プロペニルであり；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；
Ｘ^３およびＸ^４は、独立してＯまたはＳであり；Ｒ^ｘ、Ｒ^ｙ、Ｒ^ｗおよびＲ^ｚは、独立して、水素、ハロゲン、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｘ、Ｒ^ｙ、Ｒ^ｗおよびＲ^ｚは、独立して、水素、ハロゲン、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｘ、Ｒ^ｙ、Ｒ^ｗおよびＲ^ｚは、独立して、Ｃ_１〜Ｃ_６アルキル、水素、非置換フェニル、置換フェニルまたはハロゲンであり；またはＲ^ｘとＲ^ｙが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｗとＲ^ｚが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｙとＲ^ｗが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成する。 In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (II):

Where
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ¹ is carbene;
L ² is a neutral electron donor ligand;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted _C 3 _{-C 10} cycloalkyl, substituted _C 3 _{-C 10} cycloalkyl is unsubstituted _C 5 _{-C 24} aryl or substituted _C 5 _{-C 24} aryl; typically, R is methyl , Ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² Is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X ³ and X ⁴ are independently O or S; R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl. Or substituted heteroatom-containing hydrocarbyl; generally, R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl , Unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^x , R ^y , R ^w and R ^z are independently C ₁ -C ₆ alkyl, hydrogen, unsubstituted phenyl, substituted phenyl or halogen; or R ^x and R ^y are joined together to form a non- Forming a substituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic A ring or polycyclic aryl is formed; or R ^y and R ^w are joined together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (II), wherein:
M is Ru;
L ¹ is carbene;
n is 0;
m is 0;
R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are bonded together to form a 5-membered sulfoxide group Forming a ring or a 6-membered heterocyclic ring;
R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene And
X ³ and X ⁴ are each S;
R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C _{3 to} C ₁₀ cycloalkyl, unsubstituted C _{5 to} C ₂₄ aryl or substituted C _{5 to} C ₂₄ aryl; typically R ^x , R ^y , R ^w and R ^z are independently C ₁ -C ₆ alkyl, hydrogen, unsubstituted phenyl, substituted phenyl or halogen; or of R ^x and R ^y are joined together, the unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic Form an aryl; or R ^w and R ^z join together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R ^y and R ^w together To an unsubstituted bicyclic ring. To form an aryl bicyclic or polycyclic aryl or substituted polycyclic.

式中、
Ｍは、第８族遷移金属であり；一般には、Ｍは、ルテニウムまたはオスミウムであり；典型的には、Ｍは、ルテニウムであり；
Ｌ^２は、中性の電子供与配位子であり；
ｎは、０または１であり；典型的には、ｎは０であり；
ｍは、０、１または２であり；典型的には、ｍは０であり；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｂは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；Ｘ^１およびＸ^２は、独立してアニオン性配位子であり；一般には、Ｘ^１およびＸ^２は、独立して、ハロゲン、トリフルオロアセテート、ペルフルオロフェノレート、チオレート、アルキルチオ、アリールチオまたはニトレートであり；典型的には、Ｘ^１およびＸ^２は、独立して、Ｃｌ、Ｂｒ、ＩまたはＦであり；
Ｒ^１およびＲ^２は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；典型的には、Ｒ^１は水素であり、Ｒ^２は、非置換フェニル、置換フェニルまたは置換１−プロペニルであり；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；
ＸおよびＹは、独立して、Ｃ、ＣＲ^３ａ、Ｎ、Ｏ、ＳまたはＰであり；ＸまたはＹのうち１つだけが、ＣまたはＣＲ^３ａであってもよく；典型的には、ＸおよびＹは、それぞれＮであり；
Ｑ^１、Ｑ^２、Ｒ^３、Ｒ^３ａおよびＲ^４は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｑ^１、Ｑ^２、Ｒ^３、Ｒ^３ａおよびＲ^４は、場合により、非置換ヒドロカルビレン、置換ヒドロカルビレン、非置換ヘテロ原子含有ヒドロカルビレン、置換ヘテロ原子含有ヒドロカルビレンまたは−（ＣＯ）−などのリンカーを介して、ＸまたはＹに結合しており；典型的には、Ｑ^１、Ｑ^２、Ｒ^３、Ｒ^３ａおよびＲ^４は、ＸまたはＹに直接結合しており；
ＸがＯまたはＳの場合、ｐが０であり、ＸがＮ、ＰまたはＣＲ^３ａである場合、ｐが１であり、ＸがＣである場合、ｐが２であり；ＹがＯまたはＳの場合、ｑが０であり、ＹがＮ、ＰまたはＣＲ^３ａである場合、ｑが１であり、ＸがＣである場合、ｑが２である。 In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (III):

Where
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ² is a neutral electron donor ligand;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; X ¹ and X ² are independently anionic ligands; generally X ¹ and X ² is independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, Typically thiol or nitrate; typically X ¹ and X ² are independently Cl, Br, I or F;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² Is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X and Y are independently C, CR ^3a , N, O, S or P; only one of X or Y may be C or CR ^3a ; And Y are each N;
Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally Q ¹ , Q ² , R ³ , R ^3a and R ⁴ may optionally be unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene or — (CO) — Is typically attached to X or Y via a linker such as; Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are directly attached to X or Y;
When X is O or S, p is 0, when X is N, P or CR ^3a , p is 1 and when X is C, p is 2; Y is O or S In the case of q, q is 0, Y is N, P or CR ^3a , q is 1, and when X is C, q is 2.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (III), wherein:
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ² is a neutral electron donor ligand;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate Yes; typically X ¹ and X ² are independently Cl, Br, I or F; R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted A heteroatom-containing hydrocarbyl or a substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X and Y are independently C, CR ^3a , N, O, S or P; only one of X or Y may be C or CR ^3a ; And Y are each N;
Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally Q ¹ , Q ² , R ³ , R ^3a and R ⁴ may optionally be unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene or — (CO) — Is typically attached to X or Y via a linker such as; Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are directly attached to X or Y;
When X is O or S, p is 0, when X is N, P or CR ^3a , p is 1 and when X is C, p is 2; Y is O or S In the case of q, q is 0, Y is N, P or CR ^3a , q is 1, and when X is C, q is 2.

式中、
Ｍは、第８族遷移金属であり；一般には、Ｍは、ルテニウムまたはオスミウムであり；典型的には、Ｍは、ルテニウムであり；
Ｌ^２は、中性の電子供与配位子であり；ｎは、０または１であり；
ｍは、０、１または２であり；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；または、Ｒ^ａとＲ^ｂが一緒に結合して、スルホキシド基を有する５員環または６員環のヘテロ環式環を形成し；
Ｘ^１およびＸ^２は、独立してアニオン性配位子であり；
Ｒ^１およびＲ^２は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであるか；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；
ＸおよびＹは、独立して、Ｃ、ＣＲ^３ａまたはＮであり；ＸまたはＹのうち１つだけが、ＣまたはＣＲ^３ａであってもよく；
Ｒ^３ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；
Ｑは、構造−［ＣＲ^１１Ｒ^１２］_ｓ−［ＣＲ^１３Ｒ^１４］_ｔ−または−［ＣＲ^１１＝ＣＲ^１３］−を有する２原子結合であり；
Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；
「ｓ」および「ｔ」は、独立して、１または２であり；
Ｒ^３は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；
Ｒ^４は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルである。 In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (IV):

Where
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ² is a neutral electron donating ligand; n is 0 or 1;
m is 0, 1 or 2;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ^a and R ^b are bonded together to form a 5-membered ring having a sulfoxide group Or form a 6-membered heterocyclic ring;
X ¹ and X ² are independently anionic ligands;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are bonded together Form an optionally substituted indenylidene;
X and Y are independently C, CR ^3a or N; only one of X or Y may be C or CR ^3a ;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - or ^{- [CR 11 = CR 13]} - is 2 atoms bonded with;
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
“S” and “t” are independently 1 or 2;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.

In one embodiment of formula (IV), any two or more of X ¹ , X ² , L ² , R ¹ and R ² are optionally joined together to form a bidentate ligand or multidentate coordination Or a cyclic group containing a child; or any one or more of X ¹ , X ² , L ² , R ¹ and R ² may optionally be attached to the support.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (IV):
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ² is a neutral electron donor ligand; n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate Typically; typically X ¹ and X ² are independently Cl, Br, I or F;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² Is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X and Y are independently C, CR ^3a or N; only one of X or Y may be C or CR ^3a ; typically X and Y are each N Is;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene; in general, Q is a structure — [CR ¹¹ R ¹² ] _s- [CR ¹³ R ¹⁴ ] _t -or-[CR ¹¹ = CR ¹³ ]-; typically Q is-[CR ¹¹ R ¹² ] _s- [ CR ¹³ R ^14] _t - a, where ^{in, R 11, R 12, R} 13 and ^{R 14} are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom, Typically, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C ₁ -C ₁₂ alkyl, substituted C ₁ -C ₁₂ alkyl, unsubstituted C ₁ -C ₁₂ heteroalkyl, substituted C ₁ -C ₁₂ heteroalkyl, unsubstituted C ₅ -C ₁₄ aryl or substituted C ₅ -C ₁₄ aryl; “s” and “ t ”is independently 1 or 2; typically,“ s ”and“ t ”are each 1; any two of R ¹¹ , R ¹² , R ^13, and R ¹⁴ are Optionally joined together to form a substituted or unsubstituted, saturated or unsaturated ring structure;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to 3 substituents, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl, or 2-methyl-phenyl Is;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl, or 2-methyl-phenyl in it; or when X is ^{CR 3a, R 3a} and ^{R 4,} together with the carbon atoms to which they are bonded, form a cycloalkyl or heterocyclic ring of 5 to 10-membered ring It may be.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (IV), wherein:
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ² is a neutral electron donor ligand;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate Typically; typically X ¹ and X ² are independently Cl, Br, I or F;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen and R ² Is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X and Y are independently C, CR ^3a or N; only one of X or Y may be C or CR ^3a ; typically X and Y are each N Is;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene; in general, Q is a structure — [CR ¹¹ R ¹² ] _s- [CR ¹³ R ¹⁴ ] _t -or-[CR ¹¹ = CR ¹³ ]-; typically Q is-[CR ¹¹ R ¹² ] _s- [ CR ¹³ R ^14] is t-, ^{wherein, R 11, R 12, R} 13 and ^{R 14} are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom, be-containing hydrocarbyl; ^{typically, R 11, R 12, R} 13 and ^{R 14} are independently hydrogen, unsubstituted _C 1 _{-C 12} alkyl, substituted ₁ -C ₁₂ alkyl, unsubstituted _C 1 _{-C 12} heteroalkyl, substituted _C 1 _{-C 12} heteroalkyl, is unsubstituted _C 5 _{-C 14} aryl or substituted _C 5 _{-C 14} aryl; "s" and "t Is independently 1 or 2; typically, “s” and “t” are each 1; when any two of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are present Linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to 3 substituents, typically, ^{R 3} is adamantyl, 2-an iso-propyl - phenyl, 2,4,6-trimethylphenyl, 2 , 6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2-an iso-propyl - phenyl, 2 , 6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (IV), wherein:
M is Ru;
n is 0;
m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted _C 3 _{-C 10} cycloalkyl, substituted _C 3 _{-C 10} cycloalkyl is unsubstituted _C 5 _{-C 24} aryl or substituted _C 5 _{-C 24} aryl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b together To form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F;
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are joined together and optionally substituted indenylidene Forming;
X and Y are each N;
Q is — (CH ₂ —CH ₂ ) — (ie, a diatomic bond having the structure — [CR ¹¹ R ¹² ] _s — [CR ¹³ R ¹⁴ ] _t —); R ¹¹ , R ¹² , R ¹³ And R ¹⁴ are independently hydrogen; “s” and “t” are each 1);
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A C ₅ -C ₂₄ aryl substituted with up to three substituents which are al selected,
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A C ₅ -C ₂₄ aryl substituted by up to three substituents which are al selected.

式中、
Ｒ^１は、水素であり；
Ｒ^２は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；典型的には、Ｒ^２は、非置換フェニル、置換フェニル、または置換１−プロペニルであるか；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｂは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｘ^１およびＸ^２は、独立して、ハロゲン、トリフルオロアセテート、ペルフルオロフェノレート、チオレート、アルキルチオ、アリールチオまたはニトレートであり；一般には、Ｘ^１およびＸ^２は、独立して、Ｃｌ、Ｂｒ、ＩまたはＦであり；典型的には、Ｘ^１およびＸ^２は、それぞれＣｌであり；
Ｒ^３は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^３は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり、典型的には、Ｒ^３は、アダマンチル、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニル、２−ｉｓｏ−プロピル−フェニルまたは２−メチル−フェニルであり；
Ｒ^４は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^４は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、または非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^４は、２，４，６−トリメチルフェニル、２−ｉｓｏ−プロピル−フェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニルまたは２−メチル−フェニルである。 Thus, the olefin metathesis catalyst of formula (IV) can also be represented by the structure of formula (V):

Where
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl Or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to 3 substituents, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2-an iso-propyl - phenyl, 2 , 6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (V):
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl Or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group; typically, R ^a and R ^b are joined together to form a tetrahydro Forming thiophene oxide;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to 3 substituents, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2-an iso-propyl - phenyl, 2 , 6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (V):
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are joined together and optionally substituted indenylidene Forming;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently halogen;
R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or substituted C ₁ -C ₂₀ alkyl, unsubstituted C ₁ -C ₂₀ alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted C ₅ -C ₂₄ heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alk C ₅ -C ₂₄ aryl substituted with up to 3 substituents selected from reel and halide;
R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl is selected unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides C ₅ -C ₂₄ aryl substituted with up to 3 substituents.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (V):
R ¹ is hydrogen;
Is R ² unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl;
R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl; or R ^a and R ^b are joined together to form tetrahydrothiophene oxide;
X ¹ and X ² are each Cl;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl Is;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl. .

）または２−メチル−１−プロペニル（すなわち、−ＣＨ＝Ｃ（ＣＨ_３）_２または

）であり；またはＲ^１とＲ^２が一緒に結合して、３−フェニルインデン−１−イリデン（すなわち、

）を形成し；
Ｒ^ａは、水素、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチルまたはフェニルであり；
Ｒ^ｂは、水素、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチルまたはフェニルであり；
Ｘ^１およびＸ^２は、それぞれＣｌであり；
Ｒ^３は、フェニル、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、アダマンチル、２−ｉｓｏ−プロピル−フェニル、２−メチル−フェニルまたは２−イソプロピル−６−メチルフェニルであり；
Ｒ^４は、フェニル、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−ｉｓｏ−プロピル−フェニル、２−メチル−フェニルまたは２−イソプロピル−６−メチルフェニルである。 In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (V):
R ¹ is hydrogen;
R ² is phenyl, 2-iso-propoxy-phenyl (ie,

) Or 2-methyl-1-propenyl (ie, —CH═C (CH ₃ ) ₂ or

Or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene (ie,

);
R ^a is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
R ^b is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
X ¹ and X ² are each Cl;
R ³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, adamantyl, 2-iso-propyl-phenyl, 2-methyl-phenyl or 2-isopropyl-6-methylphenyl Is;
R ⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-methyl-phenyl or 2-isopropyl-6-methylphenyl. .

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (V):
R ¹ is hydrogen;
R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1-propenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ^a and R ^b are joined together to form a tetrahydrothiophene oxide having a sulfoxide group; X ¹ and X ² are each Cl;
R ³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, adamantyl, 2-iso-propyl-phenyl, 2-methyl-phenyl or 2-isopropyl-6-methylphenyl Is;
R ⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-methyl-phenyl or 2-isopropyl-6-methylphenyl. .

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (V):
R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ^a is methyl;
R ^b is methyl;
X ¹ and X ² are each Cl;
R ³ is 2,4,6-trimethylphenyl;
R ⁴ is 2,4,6-trimethylphenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of formula (V) are described in Table (1), where X ¹ is Cl and X ² is Cl.

であり、Ｍｉｐｐは、

であり、ＤＩＰＰは、

であり、アダマンチルは、

であり、ＩＰＰは、

であり、２−Ｍｅ−Ｃ_６Ｈ_５は、

であり、Ｍｅはメチルであり、ｎ−Ｂｕは、ブチル［ＣＨ_３−（ＣＨ_２）_３−］であり、Ｐｈはフェニルであり、

は、［−（ＣＨ_２）_４−］である。 In the table, Mes is

And Mipp is

And DIPP is

And adamantyl is

And IPP is

2-Me-C ₆ H ₅ is

And Me is methyl, n-Bu is butyl [CH ₃ — (CH ₂ ) ₃ —], Ph is phenyl,

Is [— (CH ₂ ) ₄ —].

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (IV), wherein:
M is Ru;
n is 0;
m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted _C 3 _{-C 10} cycloalkyl, substituted _C 3 _{-C 10} cycloalkyl is unsubstituted _C 5 _{-C 24} aryl or substituted _C 5 _{-C 24} aryl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b together To form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F;
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are joined together and optionally substituted indenylidene Forming;
X and Y are each N;
Q is — (CH═CH) — (ie, a diatomic bond having the structure — [CR ¹¹ ═CR ¹³ ] —; where R ¹¹ and R ¹³ are hydrogen); R ³ is , Unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, non substituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, non Conversion _C 6 _{-C 24} aralkyl, substituted with up to 3 substituents selected substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides C ₅ -C ₂₄ aryl,
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A C ₅ -C ₂₄ aryl substituted by up to three substituents which are al selected.

式中、
Ｒ^１は、水素であり；
Ｒ^２は、非置換フェニル、置換フェニル、または置換１−プロペニルであるか；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；または、Ｒ^ａとＲ^ｂが一緒に結合して、スルホキシド基を有する５員環または６員環のヘテロ環式環を形成し；
Ｘ^１およびＸ^２は、独立して、ハロゲン、トリフルオロアセテート、ペルフルオロフェノレート、チオレート、アルキルチオ、アリールチオまたはニトレートであり；一般には、Ｘ^１およびＸ^２は、独立して、Ｃｌ、Ｂｒ、ＩまたはＦであり；典型的には、Ｘ^１およびＸ^２は、それぞれＣｌであり；
Ｒ^３は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^３は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり、典型的には、Ｒ^３は、アダマンチル、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニル、２−ｉｓｏ−プロピル−フェニルまたは２−メチル−フェニルであり；
Ｒ^４は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^４は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、または非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^４は、２，４，６−トリメチルフェニル、２−ｉｓｏ−プロピル−フェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニルまたは２−メチル−フェニルである。 Thus, the olefin metathesis catalyst of formula (IV) can also be represented by the structure of formula (VI)

Where
R ¹ is hydrogen;
R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene; R ^a , Hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted _C 3 _{-C 10} cycloalkyl, substituted _C 3 _{-C 10} cycloalkyl is unsubstituted _C 5 _{-C 24} aryl or substituted _C 5 _{-C 24} aryl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b together To form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to 3 substituents, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2-an iso-propyl - phenyl, 2 , 6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (VI), wherein:
R ¹ is hydrogen;
R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1-propenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ^a is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
R ^b is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
X ¹ and X ² are each Cl;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (VI), wherein:
R ¹ is hydrogen;
R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently Cl, Br, I or F; typically, X ¹ and X ² are each Cl;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl Is;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl. .

Non-limiting examples of olefin metathesis catalysts represented by the structure of formula (VI) are described in Table (2), where X ¹ is Cl and X ² is Cl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (IV), wherein:
M is Ru;
n is 0;
m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of the ring;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; typically X ¹ and X ² are independently Cl, Br , I or F;
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl Or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
Y is N;
X is CR ^3a ;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ^3a and R ⁴ together with the carbon atom to which they are attached are 5-10 members May form a cycloalkyl or heterocyclic ring of the ring;
Q is a diatomic bond having the structure — [CR ¹¹ R ¹² ] _s — [CR ¹³ R ¹⁴ ] _t —; where R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen , Unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C ₁ -C ₁₂ alkyl, substituted _C 1 _{-C 12} alkyl, unsubstituted _C 1 _{-C 12} heteroalkyl, substituted _C 1 _{-C 12} heteroalkyl, unsubstituted _C 5 _{-C 14} aryl or substituted _C 5 _{-C 14} aryl “S” and “t” are each 1;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to three substituents which are,
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a C ₅ -C ₂₄ aryl substituted with up to three substituents which are al selected; or the R ^3a and R ^4, together with the carbon atoms to which they are bonded, a 5 to 10-membered cycloalkyl or heterocycloalkyl A cyclic ring may be formed.

式中、
Ｒ^１は、水素であり；
Ｒ^２は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^２は、非置換フェニル、置換フェニル、または置換１−プロペニルであるか；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；
Ｒ^ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；
Ｒ^ｂは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｂは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；または、Ｒ^ａとＲ^ｂが一緒に結合して、スルホキシド基を有する５員環または６員環のヘテロ環式環を形成し；
Ｘ^１およびＸ^２は、独立して、ハロゲン、トリフルオロアセテート、ペルフルオロフェノレート、チオレート、アルキルチオ、アリールチオまたはニトレートであり；一般には、Ｘ^１およびＸ^２は、独立して、Ｃｌ、Ｂｒ、ＩまたはＦであり；典型的には、Ｘ^１およびＸ^２は、それぞれＣｌであり；
Ｒ^３は、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^３は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり、典型的には、Ｒ^３は、アダマンチル、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−メチル−６−ｔｅｒｔ−ブチルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニル、２−ｉｓｏ−プロピル−フェニル、２，６−ジ−エチルフェニル、２−エチル−６−メチルフェニルまたは２−メチル−フェニルであり；Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、独立して、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、独立して、水素、非置換Ｃ_１〜Ｃ_１２アルキル、置換Ｃ_１〜Ｃ_１２アルキル、非置換Ｃ_１〜Ｃ_１２ヘテロアルキル、置換Ｃ_１〜Ｃ_１２ヘテロアルキル、非置換Ｃ_４〜Ｃ_１２シクロアルキル、置換Ｃ_４〜Ｃ_１２シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４ヘテロアラルキルまたは置換Ｃ_６〜Ｃ_２４ヘテロアラルキルであり；典型的には、Ｒ^１１およびＲ^１２は、それぞれメチルであり、Ｒ^１３およびＲ^１４は、それぞれ水素であり；
Ｒ^３ａは、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^３ａは、非置換Ｃ_１〜Ｃ_１２アルキル、置換Ｃ_１〜Ｃ_１２アルキル、非置換Ｃ_４〜Ｃ_１２シクロアルキル、置換Ｃ_４〜Ｃ_１２シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４ヘテロアラルキルまたは置換Ｃ_６〜Ｃ_２４ヘテロアラルキルであり；典型的には、Ｒ^３ａは、メチル、エチル、ｎ−プロピルまたはフェニルであり；
Ｒ^４は、水素、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；一般には、Ｒ^４は、非置換Ｃ_１〜Ｃ_１２アルキル、置換Ｃ_１〜Ｃ_１２アルキル、非置換Ｃ_４〜Ｃ_１２シクロアルキル、置換Ｃ_４〜Ｃ_１２シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４ヘテロアラルキルまたは置換Ｃ_６〜Ｃ_２４ヘテロアラルキルであり；典型的には、Ｒ^４は、メチル、エチル、ｎ−プロピルまたはフェニルであり；またはＲ^４とＲ^３ａとが、これらに結合する炭素原子と共に、５〜１０員環のシクロアルキルまたはヘテロ環式環を形成してもよい。 Thus, the olefin metathesis catalyst of formula (IV) can also be represented by the structure of formula (VII)

Where
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; Or, R ¹ and R ² are joined together to form an optionally substituted indenylidene;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of the ring;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, which is unsubstituted _C 5 _{-C 24} aryl, unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 ~ C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, selected from substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to 3 substituents, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl or R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; In general, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C ₁ -C ₁₂ alkyl, substituted C ₁ -C ₁₂ alkyl, unsubstituted _C 1 _{-C 12} heteroalkyl, substituted _C 1 _{-C 12} heteroalkyl, unsubstituted _C 4 _{-C 12} cycloalkyl, substituted _C 4 _{-C 12} cycloalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _{C 6} -C be ₂₄ heteroaralkyl or substituted _C 6 _{-C 24} heteroaralkyl; ^{typically, R 11} and ^{R 12} are each ^{methyl, R 13} and ^{R 14} are each hydrogen;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^3a is unsubstituted C ₁ -C ₁₂ alkyl, substituted C ₁ -C ₁₂ alkyl, unsubstituted _C 4 _{-C 12} cycloalkyl, substituted _C 4 _{-C 12} cycloalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl, unsubstituted C ₆ -C ₂₄ aralkyl, substituted C ₆ -C ₂₄ aralkyl, unsubstituted C ₆ -C ₂₄ heteroaralkyl or substituted C ₆ -C ₂₄ heteroaralkyl; typically , R ^3a is methyl, ethyl, n-propyl or phenyl;
R ⁴ is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ⁴ is unsubstituted C ₁ -C ₁₂ alkyl, substituted C ₁ -C ₁₂ alkyl, unsubstituted _C 4 _{-C 12} cycloalkyl, substituted _C 4 _{-C 12} cycloalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl, unsubstituted C ₆ -C ₂₄ aralkyl, substituted C ₆ -C ₂₄ aralkyl, unsubstituted C ₆ -C ₂₄ heteroaralkyl or substituted C ₆ -C ₂₄ heteroaralkyl; typically , ^{R 4} is methyl, ethyl, n- propyl or phenyl; or ^{R 4} and ^{R 3a,} binding thereto Together with the carbon atoms to, they may form a cycloalkyl or heterocyclic ring of 5 to 10-membered ring.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (VII):
R ¹ is hydrogen;
R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1-propenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ^a is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
R ^b is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl; X ¹ and X ² are each Cl;
R ³ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, 2,6-di-ethyl Phenyl, 2-methyl-6-tert-butylphenyl, 2-ethyl-6-methylphenyl or 2-methyl-phenyl;
R ¹¹ and R ¹² are each methyl;
R ¹³ and R ¹⁴ are each hydrogen;
R ^3a is methyl, ethyl, n-propyl or phenyl;
R ⁴ is methyl, ethyl, n-propyl or phenyl; or R ^3a and R ⁴ together with the carbon atom to which they are attached, a 5-, 6- or 10-membered cycloalkyl or heterocycle Form a formula ring.

A non-limiting example of an olefin metathesis catalyst represented by the structure of formula (VII) is set forth in Table (3), where X ¹ is Cl, X ² is Cl, and R ¹¹ is methyl. Yes, R ¹² is methyl, R ¹³ is hydrogen, and R ¹⁴ is hydrogen.

である。 In the table, EMP is

It is.

であり；
Ｘ^３およびＸ^４は、独立して、ＯまたはＳであり；
Ｒ^ｘ、Ｒ^ｙ、Ｒ^ｗおよびＲ^ｚは、独立して、水素、ハロゲン、非置換ヒドロカルビル、置換ヒドロカルビル、非置換ヘテロ原子含有ヒドロカルビル、または置換ヘテロ原子含有ヒドロカルビルであり；またはＲ^ｘとＲ^ｙが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｗとＲ^ｚが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｙとＲ^ｗが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成する。 In another embodiment of formula (IV), the present invention provides an olefin metathesis catalyst, wherein:
M is a Group 8 transition metal; generally M is ruthenium or osmium; typically, M is ruthenium;
L ² is a neutral electron donor ligand;
n is 0 or 1; typically, n is 0;
m is 0, 1 or 2; typically, m is 0;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom be-containing hydrocarbyl; typically, ^{R b} is unsubstituted _C 1 _{-C 10} Alkyl, substituted _C 1 _{-C 10} alkyl, unsubstituted _C 3 _{-C 10} cycloalkyl, substituted _C 3 _{-C 10} cycloalkyl is unsubstituted _C 5 _{-C 24} aryl or substituted _C 5 _{-C 24} aryl; typically R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are bonded together to form a sulfoxide group. Forming a 5- or 6-membered heterocyclic ring having;
X and Y are independently C, CR ^3a or N; only one of X or Y may be C or CR ^3a ;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - or ^{- [CR 11 = CR 13]} - is 2 atoms bonded with;
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
“S” and “t” are independently 1 or 2;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are joined together, Forming an optionally substituted indenylidene;
That part

Is;
X ³ and X ⁴ are independently O or S;
R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ^x and R ^y Are joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z are joined together to form an unsubstituted bicyclic or Forming a polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^y and R ^w are joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic Aryl is formed.

であり；
Ｘ^３およびＸ^４は、それぞれＳであり；
Ｒ^ｘ、Ｒ^ｙ、Ｒ^ｗおよびＲ^ｚは、独立して、Ｃ_１〜Ｃ_６アルキル、水素、ハロゲン、非置換フェニルまたは置換フェニルであり；一般には、Ｒ^ｘは、メチル、水素またはＣｌであり、Ｒ^ｙは、水素であり、Ｒ^ｗは、水素であり、Ｒ^ｚは、Ｃｌ、ｎ−ブチル、水素またはフェニルであり；またはＲ^ｘとＲ^ｙが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｗとＲ^ｚが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｙとＲ^ｗが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成する。 In another embodiment of formula (IV), the present invention provides an olefin metathesis catalyst, wherein:
M is Ru;
n is 0;
m is 0;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted Typically C ₅ -C ₂₄ aryl; typically R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted Typically C ₅ -C ₂₄ aryl; typically R ^b is methyl, ethyl, n-propyl, iso-propyl, t-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X and Y are each N;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - is 2 atoms bonded with;
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently C ₁ -C ₆ alkyl or hydrogen; generally R ¹¹ is hydrogen or methyl, R ¹² is hydrogen or methyl, R ¹³ is hydrogen and R ¹⁴ is hydrogen; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each hydrogen;
“S” and “t” are each 1;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene And
That part

Is;
X ³ and X ⁴ are each S;
R ^x , R ^y , R ^w and R ^z are independently C ₁ -C ₆ alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; in general, R ^x is methyl, hydrogen or Cl R ^y is hydrogen, R ^w is hydrogen, R ^z is Cl, n-butyl, hydrogen or phenyl; or R ^x and R ^y are bonded together to form an unsubstituted Forming a bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or Forming a polycyclic aryl; or R ^y and R ^w are joined together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

式中、
Ｒ^ａは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ａは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；Ｒ^ｂは、非置換Ｃ_１〜Ｃ_１０アルキル、置換Ｃ_１〜Ｃ_１０アルキル、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールまたは置換Ｃ_５〜Ｃ_２４アリールであり；典型的には、Ｒ^ｂは、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはフェニルであり；または、Ｒ^ａとＲ^ｂが一緒に結合して、スルホキシド基を有する５員環または６員環のヘテロ環式環を形成し；
Ｒ^３は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり、典型的には、Ｒ^３は、アダマンチル、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−メチル−６−ｔｅｒｔ−ブチルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニル、２−ｉｓｏ−プロピル−フェニル、２，６−ジ−エチルフェニル、２−エチル−６−メチルフェニル、２，４，６−トリフルオロフェニル、２，６−ジフルオロフェニル；
３．５−ジ−ｔｅｒｔ−ブチルフェニル、２，４−ジメチルフェニルまたは２−メチル−フェニルであり；
Ｒ^４は、非置換Ｃ_３〜Ｃ_１０シクロアルキル、置換Ｃ_３〜Ｃ_１０シクロアルキル、非置換Ｃ_５〜Ｃ_２４アリールであるか、非置換Ｃ_１〜Ｃ_２０アルキル、置換Ｃ_１〜Ｃ_２０アルキル、非置換Ｃ_１〜Ｃ_２０ヘテロアルキル、置換Ｃ_１〜Ｃ_２０ヘテロアルキル、非置換Ｃ_５〜Ｃ_２４アリール、置換Ｃ_５〜Ｃ_２４アリール、非置換Ｃ_５〜Ｃ_２４ヘテロアリール、置換Ｃ_５〜Ｃ_２４ヘテロアリール、非置換Ｃ_６〜Ｃ_２４アラルキル、置換Ｃ_６〜Ｃ_２４アラルキル、非置換Ｃ_６〜Ｃ_２４アルカリール、置換Ｃ_６〜Ｃ_２４アルカリールおよびハロゲン化物から選択される３個までの置換基で置換されたＣ_５〜Ｃ_２４アリールであり、典型的には、Ｒ^４は、２，４，６−トリメチルフェニル、２，６−ジ−ｉｓｏ−プロピルフェニル、２−メチル−６−ｔｅｒｔ−ブチルフェニル、２−ｉｓｏ−プロピル−６−メチルフェニル、２−ｉｓｏ−プロピル−フェニル、
２．６−ジ−エチルフェニル、２−エチル−６−メチルフェニル、２，４，６−トリフルオロフェニル、２，６−ジフルオロフェニル、３，５−ジ−ｔｅｒｔ−ブチルフェニル、２，４−ジメチルフェニルまたは２−メチル−フェニルであり；
Ｒ^１は水素であり、Ｒ^２は、非置換フェニル、置換フェニルまたは置換１−プロペニルであり；または、Ｒ^１とＲ^２が一緒に結合して、場合により置換されていてもよいインデニリデンを形成し；
Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、独立して、Ｃ_１〜Ｃ_６アルキルまたは水素であり；一般には、Ｒ^１１は水素またはメチルであり、Ｒ^１２は水素またはメチルであり、Ｒ^１３は水素であり、Ｒ^１４は水素であり；典型的には、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、独立して、水素であり；
Ｒ^ｘ、Ｒ^ｙ、Ｒ^ｗおよびＲ^ｚは、独立して、Ｃ_１〜Ｃ_６アルキル、水素、ハロゲン、非置換フェニルまたは置換フェニルであり；一般には、Ｒ^ｘは、メチル、水素またはＣｌであり、Ｒ^ｙは、水素であり、Ｒ^ｗは、水素であり、Ｒ^ｚは、Ｃｌ、ｎ−ブチル、水素またはフェニルであり；またはＲ^ｘとＲ^ｙが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｗとＲ^ｚが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成し；またはＲ^ｙとＲ^ｗが一緒に結合して、非置換の二環または多環のアリールまたは置換の二環または多環のアリールを形成する。 Thus, the olefin metathesis catalyst of formula (IV) can also be represented by the structure of formula (VIII)

Where
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted Typically C ₅ -C ₂₄ aryl; typically R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted _C 1 _{-C 10} alkyl, unsubstituted _C 3 _{-C 10} cycloalkyl, substituted _C 3 _{-C 10} cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or substituted _C 5 _{-C 24} aryl Typically, R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenoxy; Or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} 3 selected from alkaryl and halide a _C 5 _{-C 24} aryl substituted with up to pieces, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6 Methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl;
3.5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} 3 selected from alkaryl and halide a _C 5 _{-C 24} aryl substituted with up to pieces, typically, ^{R 4} is 2,4,6-trimethylphenyl, 2,6-di -iso- Pro Butylphenyl, 2-methyl -6-tert-butylphenyl, 2-an iso-propyl-6-methylphenyl, 2-an iso-propyl - phenyl,
2.6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4- Dimethylphenyl or 2-methyl-phenyl;
R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene And
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently C ₁ -C ₆ alkyl or hydrogen; generally R ¹¹ is hydrogen or methyl, R ¹² is hydrogen or methyl, R ¹³ is hydrogen and R ¹⁴ is hydrogen; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen;
R ^x , R ^y , R ^w and R ^z are independently C ₁ -C ₆ alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; in general, R ^x is methyl, hydrogen or Cl R ^y is hydrogen, R ^w is hydrogen, R ^z is Cl, n-butyl, hydrogen or phenyl; or R ^x and R ^y are bonded together to form an unsubstituted Forming a bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or Forming a polycyclic aryl; or R ^y and R ^w are joined together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In one embodiment, the present invention provides an olefin metathesis catalyst represented by the structure of formula (VIII):
R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are bonded together to form a 5-membered sulfoxide group Forming a ring or a 6-membered heterocyclic ring;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2- iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethyl Phenyl, 2,6-difluorophenyl or 2-methyl-phenyl;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso- Propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl or 2-methyl-phenyl;
R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene And
R ¹¹ is hydrogen or methyl, R ¹² is hydrogen or methyl, R ¹³ is hydrogen, R ¹⁴ is hydrogen; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are Each hydrogen;
R ^x is methyl, hydrogen or Cl, R ^y is hydrogen, R ^w is hydrogen and R ^z is Cl, n-butyl, hydrogen or phenyl; or R ^x and R ^y Are joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z are joined together to form an unsubstituted bicyclic or Forming a polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^y and R ^w are joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic Aryl is formed.

Non-limiting examples of olefin metathesis catalysts represented by the structure of formula (VIII) are listed in Table (4), where R ^a is methyl, R ^b is methyl, and R ¹¹ is hydrogen. Yes, R ¹² is hydrogen, R ¹³ is hydrogen, R ¹⁴ is hydrogen, R ^y is hydrogen, and R ^w is hydrogen.

The present invention also relates to a process for synthesizing the olefin metathesis catalyst of the present invention. The olefin metathesis catalysts of the present invention can be prepared analogously to conventional methods as understood by those skilled in the art of synthetic organic chemistry. For example, synthetic scheme 1 is shown below and shows how the compounds of the present invention can be prepared.

In a typical procedure, an olefin metathesis catalyst of general formula (A) is reacted with tosyl chloride (TsCl) and an excess of a sulfoxide derivative (R ^a R ^b SO) at room temperature to give an olefin metathesis catalyst of general formula (V). Manufacturing the formula,
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; Or, R ¹ and R ² join together to form an optionally substituted indenylidene; typically R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl- 1-propenyl; or R ¹ and R ² are joined together to form 3-phenyl-1-indenylidene;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso - propylphenyl, 2-an iso-propyl-6-methylphenyl, 2-an iso-propyl - phenyl or 2-methyl - phenyl; ^{R 4} is an unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or, Substituted heteroatom-containing hydrocarbyls; generally R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroar- Alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, be a _C 5 _{-C 24} aryl substituted with up to three substituents selected from substituted _C 6 _{-C 24} alkaryl, and halides; typically Specifically, R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl. -Phenyl;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of the ring;
R ^{j, R l} and ^{R o} are each independently a substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 1 _{-C 10} alkyl or unsubstituted _C 1 _{-C 10} alkyl In general, R ^j , R ¹ and R ^o are each independently unsubstituted C ₅ -C ₂₄ aryl; typically, R ^j , R ¹ and R ^o are each phenyl.

  In another embodiment, the present invention relates to a method of using the olefin metathesis catalyst of the present invention in the synthesis of related olefin metathesis catalysts. The ruthenium olefin metathesis catalysts having labile sulfoxide ligands of the present invention are excellent precursors for various second generation Grubbs ruthenium olefin metathesis catalysts. Second generation Grubbs ruthenium olefin metathesis catalysts synthesized during these procedures are obtained in higher yields and higher purity, which provides advantages compared to existing synthetic procedures.

For example, Synthesis Scheme 2 is shown below and illustrates how an olefin metathesis catalyst of formula (F) can be synthesized from an olefin metathesis catalyst of formula (IV).

In a typical procedure, as shown in Scheme 2, the sulfoxide ligand of the olefin metathesis catalyst represented by formula (IV) is replaced with a neutral electron donor “L” ligand. Can do. R ¹ , R ² , R ³ , R ⁴ , R, X ¹ , X ² , M, Q, n, m, R ^a , R ^b and L ² are as described herein. “L” is sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, carboxyl, nitrosyl, pyridine, thioether, Grubbs-Hoveyda ligand, trimethylphosphine (PMe ₃ ), triethylphosphine (PEt ₃ ), tri -n- butyl phosphine _(PBu 3), tri (ortho - tolyl) phosphine (P-o-tolyl _3), tri -tert- butylphosphine _(P-tert-Bu 3), tricyclopentylphosphine _(PCp 3), tri tricyclohexylphosphine _(PCy 3), triisopropyl phosphine _{(P-i-Pr 3)} , trioctylphosphine (POct _3), triisobutyl phosphine _{(P-i-Bu 3)} , triphenylphosphine _(PPh 3), tri Pentafluorophenyl) phosphine _{(P (C 6 F 5)} 3), methyl diphenyl phosphine (PMePh _2), dimethylphenylphosphine _(PMe 2 Ph), diethyl phenyl phosphine _(PEt 2 Ph), phosphabicyclo cycloalkane (e.g., mono Substituted 9-phosphabicyclo- [3.3.1] nonane, mono-substituted 9-phosphabicyclo [4.2.1] nonane, cyclohexylfoban, isopropylfoban, ethylfoban, methylfoban, butylfoban, pentylfoban) Pyridine, 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5 -Dichloropyridine, 2,4,6-trick Lopyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl- 4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-di-iso-propylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4- ( tert-butyl) pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2 , 4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H -Imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta (b) pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline , Naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolinylmine, purine, benzimidazole, bisimidazole, phenazine, acridine, carbazole, sulfur-containing heterocycles (eg, thiophene, 1,2-dithiol, 1,3 -Dithiol, thiepine, benzo (b) thiophene, benzo (c) thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, thioanthrene), oxygen-containing Heterocycle (for example, 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman -4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxane, dibenzofuran), mixed (eg, isoxazole, oxazole, thiazole, isothiazole, 1,2,3- Oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1, 2,3-dioxazole, 3H-1,2-oxathiol, 1,3-oxathiol, 4H-1,2-oxy Gin, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isoxazine, phenoxazine, phenothiazine, pyrano [3,4-b] pyrrole, indoxazine, benzoxazole, Anthranils and morpholines), aromatic nitrogen-containing and oxygen-containing heterocycles, consisting of monocyclic n-heteroaryl ligands optionally substituted with 1 to 3, preferably 1 or 2 substituents Selected from the group.

  The ligand exchange reaction is performed under an inert atmosphere (under nitrogen or argon). This reaction is generally carried out at room temperature, or 15 ° C to 25 ° C, or 25 ° C to 60 ° C, or 35 ° C to 50 ° C, or 20 ° C to 25 ° C, or 30 ° C to 40 ° C, or 25 ° C to 45 ° C. Performed at a temperature of ° C Reaction times vary from minutes to hours, 12 hours, 24 hours or 48 hours. In general, the reaction is carried out such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl ether, dioxolane, alcohol, methyl-tetrahydrofuran, acetone, ethyl acetate, methyl tert-butyl ether (MTBE), dimethylformamide (DMF) and dichloromethane. Occurs in a solvent.

In another embodiment, the invention also relates to a process for synthesizing an olefin metathesis catalyst of formula (B) starting from an olefin metathesis catalyst of formula (V).

In a typical procedure, the sulfoxide ligand of the olefin metathesis catalyst represented by formula (V) is reacted with PR ^d R ^e at room temperature in an inert solvent (eg, dichloromethane or toluene) as shown in Scheme 3. Exchange with OR ^f ligand.
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; Or, R ¹ and R ² join together to form an optionally substituted indenylidene; typically R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl- 1-propenyl; or R ¹ and R ² are joined together to form 3-phenyl-1-indenylidene;
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, t-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of rings; typically, R ^a and R ^b are joined together to form tetrahydrothiophene oxide And
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso -Propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ^d is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C _{3 to} C ₈ cycloalkyl; generally R ^d is unsubstituted C _{1 to} C ₁₀ alkyl or unsubstituted C _{6 to} C ₁₀ aryl; typically, R ^d is phenyl;
R ^e is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C _{3 to} C ₈ cycloalkyl; generally, R ^e is unsubstituted C _{1 to} C ₁₀ alkyl or unsubstituted C _{6 to} C ₁₀ aryl; typically, R ^e is phenyl;
R ^f is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C be ₃ -C ₈ cycloalkyl; generally, the ^{R f,} an unsubstituted _C 1 _{-C 10} alkyl, unsubstituted _C 6 _{-C 10} aryl, or unsubstituted _C 6 _{-C 10} aryl; typically, ^{R f} Is phenyl, methyl, p- (OMe) phenyl, iso-propyl or ethyl.

In another embodiment, the invention also relates to a process for synthesizing an olefin metathesis catalyst of formula (C) starting from an olefin metathesis catalyst of formula (V).

In a typical procedure, as shown in Scheme 4, the sulfoxide ligand of the olefin metathesis catalyst represented by formula (V) is reacted with PR ^g OR ^{h in} an inert solvent (eg, dichloromethane or toluene) at room temperature. Exchange with OR ^I ligand.
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; Or, R ¹ and R ² join together to form an optionally substituted indenylidene; typically R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl- 1-propenyl; or R ¹ and R ² are joined together to form 3-phenyl-1-indenylidene;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of rings; typically, R ^a and R ^b are joined together to form tetrahydrothiophene oxide And
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso -Propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ^g is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C ₃ -C ₈ cycloalkyl; in general, ^{R g} is unsubstituted _C 1 _-C be ₁₀ alkyl or unsubstituted _C 6 _{-C 10} aryl; typically, ^{R g} is phenyl;
R ^h is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C _{3 to} C ₈ cycloalkyl; generally R ^h is unsubstituted C _{1 to} C ₁₀ alkyl or unsubstituted C _{6 to} C ₁₀ aryl; typically R ^h is phenyl or methyl ;
R ¹ is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C _{3 to} C ₈ cycloalkyl; generally R ¹ is unsubstituted C _{1 to} C ₁₀ alkyl or unsubstituted C _{6 to} C ₁₀ aryl; typically R ¹ is phenyl or methyl .

In another embodiment, the invention also relates to a process for synthesizing an olefin metathesis catalyst of formula (D) starting from an olefin metathesis catalyst of formula (V).

In a typical procedure shown in Scheme 5, the sulfoxide ligand of the olefin metathesis catalyst represented by formula (V) is exchanged with a Grubbs-Hoveyda ligand in ethyl acetate at 60 ° C. Where
R ¹ is hydrogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; Or, R ¹ and R ² join together to form an optionally substituted indenylidene; typically R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl- 1-propenyl; or R ¹ and R ² are joined together to form 3-phenyl-1-indenylidene;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of rings; typically, R ^a and R ^b are joined together to form tetrahydrothiophene oxide And
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso -Propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ^k is hydrogen, halogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR ^s ₂ , —NHC (O) CF ₃ , —NHC (O) C ₆ F ₅ , —NHC (O) OtBu , Unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ^k is hydrogen;
R ¹ is hydrogen, halogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR ^s ₂ , —NHC (O) CF ₃ , —NHC (O) C ₆ F ₅ , —NHC (O) OtBu , Unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹ is hydrogen;
R ^m is hydrogen, _{^{halogen, -NO 2, -CN, -CF 3}} , -SO 2 NR s 2, -NHC (O) CF 3, -NHC (O) C 6 F 5, -NHC (O) OtBu , Unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ^m is hydrogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR _{^{s 2, -NHC (O) CF}} 3, be -NHC _(O) C 6 _{F 5} or -NHC (O) OtBu; preferably, ^{R m} is hydrogen;
R ⁿ is hydrogen, halogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR ^s ₂ , —NHC (O) CF ₃ , —NHC (O) C ₆ F ₅ , —NHC (O) OtBu , Unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ⁿ is hydrogen;
R ^s is hydrogen or C ₁ -C ₆ alkyl; typically R ^s is hydrogen, methyl, ethyl or n-propyl;
R ^q is unsubstituted hydrocarbyl or substituted hydrocarbyl; generally R ^q is C ₁ -C ₁₀ alkyl; typically R ^q is iso-propyl.

In another embodiment, the present invention also relates to a process for synthesizing an olefin metathesis catalyst of formula (E) starting from an olefin metathesis catalyst of formula (V).

In a typical procedure, as shown in Scheme 6, the sulfoxide ligand of the olefin metathesis catalyst represented by formula (V) is reacted with P (R ^q at room temperature in an inert solvent (eg, dichloromethane or toluene). ) Exchange with ₃ ligands. Where
R ¹ is halogen;
R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; Or, R ¹ and R ² join together to form an optionally substituted indenylidene; typically R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl- 1-propenyl; or R ¹ and R ² are joined together to form 3-phenyl-1-indenylidene;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^a is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; typically R ^b is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b bonded together to form a 5- or 6-membered ring having a sulfoxide group Forming a heterocyclic ring of rings; typically, R ^a and R ^b are joined together to form tetrahydrothiophene oxide And
X ¹ and X ² are independently halogen, trifluoroacetate, perfluorophenolate, thiolate, alkylthio, arylthio or nitrate; in general, X ¹ and X ² are independently Cl, Br, I Or F; typically, X ¹ and X ² are each Cl;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides A _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected, typically, ^{R 3} is adamantyl, 2,4,6-trimethylphenyl, 2,6-di -iso -Propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted _C 5 _{-C 24} aryl or where unsubstituted _C 1 _{-C 20} alkyl, substituted _C 1 _{-C 20} alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroaryl alkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted _C 5 _{-C 24} heteroaryl, unsubstituted _C 6 _{-C 24} aralkyl, substituted _{C 6} -C ₂₄ aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides Be a _C 5 _{-C 24} aryl substituted with up to three substituents which are al selected; typically, ^{R 4} is 2,4,6-trimethylphenyl, 2,6-di -iso- propyl Phenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl;
R ^p is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C be ₃ -C ₈ cycloalkyl; typically, ^{R p} is a substituted _C 6 _{-C 10} aryl, unsubstituted _C 6 _{-C 10} aryl, substituted _C 3 -C ₈ cycloalkyl or unsubstituted _C 3 -C ₈ cycloalkyl Typically; R ^p is phenyl, cyclohexyl or cyclopentyl.

  At this stage, one skilled in the art will appreciate that many additional compounds within the scope of the present invention can be prepared by performing various common chemical reactions. Details of specific chemical transformations are given in the examples.

  Metal carbene olefin metathesis catalysts can be utilized for olefin metathesis reactions according to techniques known in the art. For example, the metal carbene olefin metathesis catalyst is typically added to the resin composition as a solid, liquid or suspension. If the metal carbene olefin metathesis catalyst is added to the resin composition as a suspension, the metal carbene olefin metathesis catalyst may be dispersed carrier (eg, mineral oil, paraffin oil, soybean oil, tri-iso-propylbenzene), or high enough Suspend in any hydrophobic liquid that has viscosity, can disperse the catalyst effectively, is sufficiently inert and does not act as a low boiling impurity in the olefin metathesis reaction . It will be appreciated that the catalyst used in the reaction (ie, “catalyst retention”) depends on various factors such as the attributes of the reactants used and the reaction conditions. Accordingly, it is understood that the catalyst retention can be optimally selected independently for each reaction. In general, however, the catalyst can be as low as about 0.1 ppm, 1 ppm or 5 ppm to as much as about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm or 1000 ppm relative to the amount of olefin substrate (eg, cyclic olefin). Will exist in quantities ranging up to.

Cyclic Olefin The resin composition usable in the present invention disclosed herein contains one or more cyclic olefins. Such cyclic olefins may optionally be substituted by, optionally contain heteroatoms, monounsaturated, may be a C ₅ -C ₂₄ hydrocarbon di or polyunsaturated, It may be monocyclic, bicyclic or polycyclic. If the cyclic olefin can be precipitated during the ROMP reaction, either individually or as part of a ROMP cyclic olefin composition, the cyclic olefin is generally free of any strained cyclic olefin or strain. It may be a cyclic olefin.

Thus, examples of bicyclic and polycyclic olefins include, but are not limited to, dicyclopentadiene (DCPD); trimers and other higher order cyclopentadiene oligomers, including but not limited to tricyclopentadiene (cyclopentadientomer), containing cyclopentadiene tetramer and cyclopentadiene pentamer; ethylidenenorbornene; di cyclohexadiene; _norbornene; C 2 _{-C 12} hydrocarbyl substituted norbornene; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl -2 -Norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbo 5-propenyl-2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 6-dimethyl-2-norbornene; 5-phenyl norbornene; 5-benzyl norbornene; 5-acetyl norbornene; 5-methoxycarboxyl norbornene; 5-ethoxycarboxyl-1-norbornene; 5-methyl-5-methoxy-carboxyl norbornene; Bicyclo [2.2.1] hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo- 5,6-dimethoxynor Endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarboxyl norbornene; endo, endo-5,6-dimethoxycarboxyl norbornene; 2,3-dimethoxynorbornene; norbornadiene; Tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarboxyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; Pentacyclopentadecene; pentacyclohexadecene; bicyclo [2.2.1] hept-2-ene-5-phenoxymethyl; 2-ethylhexyl ester-bicyclo [2.2.1] hept-5-ene-2-carboxylic acid Acid; 2-hydride Roxyethyl ester-bicyclo [2.2.1] hept-5-ene-2-carboxylic acid; bicyclo [2.2.1] hept-5-ene-2-methanol; bicyclo [2.2.1] hepta -5-ene-2-heptanoic acid-methyl ester; bicyclo [2.2.1] hept-5-ene-2-hexanoic acid-methyl ester; 1,4: 5,8-dimethananaphthalene, 2-hexyl -1,2,3,4,4a, 5,8,8a-octahydro; bicyclo [2.2.1] hept-5-en-2-octanoic acid-methyl ester; 1,4: 5,8-di Methanonaphthalene; 2-butyl-1,2,3,4,4a, 5,8,8a-octahydro; ethylidenetetracyclododecene; 2-vinyl-1,2,3,4,4a, 5,8,8a -Octahydro-1,4: 5,8-dimethano Such Futaren, and structural isomers thereof, stereoisomers and mixtures thereof.

Experimental Section General Information-Materials and Methods In the examples below, efforts have been made to ensure accuracy with respect to numbers used (eg, amounts, temperatures, etc.), but some experimental errors and Deviations should also be considered. These examples should not be construed as limiting the invention described herein. Surprisingly, the olefin metathesis catalyst of the present invention was obtained only in the cis conformation, and trace amounts of trans stereoisomers were not detected.

  All reactions involving metal complexes were carried out using standard Schlenk techniques in oven-dried glassware under an argon or nitrogen atmosphere. Chemicals and solvents were obtained from Sigma-Aldrich, Strem, Alfa Aesar, Nexus, Brenntag, AG Layne, and TCI. Commercial reagents were used as received unless otherwise specified. Silica gel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

The crystal structure was measured at 100 (2) K using a Bruker APEX-II CCD area detector diffractometer (Mo-Kα radiation, λ = 0.10773Å). In each case, an appropriate size and quality specimen was selected and attached to a nylon loop. The structure was elucidated by direct methods, and most of the non-hydrogen atoms were successfully arranged. Semi-empirical absorbance correction was applied. Subsequent modifications with F ² using the SHELXTL / PC package (version 6.1) allowed the placement of the remaining non-hydrogen atoms.

  Ultrane® 99 dicyclopentadiene (DCPD) was obtained from Cymetech Corporation. A modified DCPD base resin (DCPD-HT) containing 20-25% tricyclopentadiene (and a small amount of higher order cyclopentadiene homolog) is generally described in US Pat. No. 4,899,005. As described above, Ultrane® 99 DCPD was prepared by heat treatment.

  Catalysts C931, C933, C793, C827, C705, C727, C748 and C848 were prepared using known methods.

¹ H and ¹³ C NMR spectra were recorded on a Varian 400 MHz spectrometer. Chemical shifts are recorded in ppm from Me ₄ Si downfield using the residual solvent peak as an internal standard (CDCl ₃ δ 7.24 ppm). The spectra were analyzed and processed using MestReNova software.

  General GC method conditions: injection temperature, 250 ° C .; detector temperature, 280 ° C .; oven temperature, starting temperature, 100 ° C .; holding time, 1 minute, up to 250 ° C. at a rising rate of 10 ° C./minute, holding time of 12 Min; the carrier gas is helium.

  GC method 1: Column: DB-225, 30 mx 0.25 mm (ID) x 0.25 µm film thickness. Manufacturer: Agilent; GC and column conditions: injector temperature: 220 ° C., detector temperature: 220 ° C .; oven temperature: starting temperature: 35 ° C., retention time: 0.5 minutes.

  Up to 130 ° C. at a rising rate of 10 ° C./min, holding time: 0 minutes. Up to 220 ° C. at a rising rate of 20 ° C./min, holding time: 5 minutes. Carrier gas: helium. Average gas velocity: 25 cm / sec. Split ratio: 20: 1.

In the examples, the following abbreviations are used.

Example 1

  A 20 mL scintillation vial was fitted with a magnetic stir bar, to which C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.268 mmol), dimethyl sulfoxide (0.210 g, 2.68 mmol) And dichloromethane (4 mL) was added. The reaction was stirred for 1 h then filtered through a celite plug and combined with diethyl ether (30 mL). The resulting black precipitate was isolated by filtration, washed with diethyl ether (2 × 10 mL) and then dried under high vacuum to give C747 as a black powder (0.346 g, 86.3% yield). ). The X-ray structure of C747 is shown in FIG.

¹ H NMR (400 MHz, CDCh): δ 8.68 (d, J = 7.4 Hz, 1H), 7.71 (d, J = 7.6 Hz, 2H), 7.52 (t, J = 7. 1 Hz, 1H), 7.42 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.4 Hz, 1H), 7.25 (t, J = 7.1 Hz, 1H), 7.11 (d, J = 6.1 Hz, 2H), 7.04 (d, J = 7.0 Hz, 1H), 6.86 (s, 1H), 6.26 (d, J = 3.8 Hz) , 2H), 4.13 to 3.99 (m, 1H), 3.99 to 3.80 (m, 2H), 3.80 to 3.69 (m, 1H), 2.82 (s, 3H) ), 2.69 (s, 3H), 2.68 (s, 3H), 2.41 (s, 3H), 2.35 (s, 3H), 2.11 (s, 3H), 2.05 (S, 3H), 1.77 ( , 3H).

(Example 2)

A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C848 (0.500 g, 0.589 mmol), p-toluenesulfonyl chloride (0.056 g, 0.30 mmol), dimethyl sulfoxide (0.230 g, 2.94 mmol). And dichloromethane (4 mL) was added. The reaction was stirred at ambient temperature for 1 hour, then filtered through a celite plug and combined with diethyl ether (30 mL). The resulting purple precipitate was isolated by filtration, washed with diethyl ether (2 × 10 mL), and then dried under high vacuum to give C647 _m as a purple crystalline solid (0.269 g, yield 70 .7%). The X-ray structure of C647 _m is shown in FIG.

¹ H NMR (400 MHz, C ₆ D ₆ ) δ 16.03 (s, 1H), 8.15 (d, J = 25.0 Hz, 2H), 7.21 (t, J = 7.3 Hz, 1H) , 7.00 (t, J = 7.8 Hz, 2H), 6.84 (s, 1H), 6.75 (s, 1H), 6.65 (s, 1H), 6.17 (s, 1H) ), 3.33 to 3.00 (m, 4H), 2.87 (s, 3H), 2.67 (s, 3H), 2.61 (s, 3H), 2.22 (s, 3H) 2.14 (s, 3H), 2.07 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H).

(Example 3)

  A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C933 (0.500 g, 0.536 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), dimethyl sulfoxide (0.209 g, 2.68 mmol) And ethyl acetate (10 mL) was added. The reaction was stirred at ambient temperature for 3 hours, resulting in a blue-gray precipitate. The solid was isolated by filtration, washed with ethyl acetate (2 x 5 mL) and then dried under high vacuum to give C731 as a blue-gray solid (0.148 g, 37.8% yield).

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 16.16 (s, 1H), 7.99 (s, 2H), 7.31-7.01 (m, 6H), 6.94 (t, 7.2 Hz, 2H), 6.65 (d, J = 7.2 Hz, 1H), 4.63-4.48 (m, 1H), 4.07-3.92 (m, 1H), 3. 76-3.60 (m, 2H), 3.60-3.44 (m, 3H), 3.42-3.27 (m, 1H), 1.97 (s, 3H), 1.87 ( d, J = 6.0 Hz, 3H), 1.72 (s, 3H), 1.67 (d, J = 6.7 Hz, 3H), 1.65 (d, J = 6.8 Hz, 3H), 1.20 (d, J = 6.3 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H), 1.04 (d, J = 6.1 Hz, 3H), 0.88 (d , J = 6.5 Hz, 3H), 0 77 (d, J = 5.7Hz, 3H).

Example 4

  A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C793 (0.500 g, 0.631 mmol), p-toluenesulfonyl chloride (0.060 g, 0.32 mmol), dimethyl sulfoxide (0.246 g, 3.15 mmol) And methyl tert-butyl ether (10 mL) was added. The reaction was stirred at ambient temperature for 4 hours, resulting in a purple precipitate. The solid was isolated by filtration and then recrystallized from dichloromethane and diethyl ether. The resulting purple crystals were isolated by filtration, washed with diethyl ether (2 x 5 mL) and then dried under high vacuum to give C591 as a purple crystalline solid (0.234 g, 62. yield). 7%). Two isomers [87:13] (not stereoisomers) were observed in solution.

¹ H NMR (400 MHz, CD ₂ CI ₂ , main isomer) δ 15.82 (s, 1H), 8.72 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 7 .5 Hz, 2H), 7.56 (dd, J = 16.6, 8.1 Hz, 2H), 7.52-7.39 (m, 2H), 7.24 (t, J = 7.9 Hz, 3H), 7.15 (d, J = 7.9 Hz, 1H), 6.96 (t, J = 7.5 Hz, 1H), 6.45 (t, J = 7.6 Hz, 1H), 4. 59-4.47 (m, 1H), 4.22 (q, J = 10.1 Hz, 1H), 3.90 (q, J = 10.4 Hz, 1H), 3.83-3.72 (m , 1H), 2.67 (s, 3H), 2.59 (s, 3H), 2.29 (s, 3H), 1.90 (s, 3H).

¹ H NMR (400 MHz, CD ₂ CI ₂ , minor isomer, selected resonance) δ 16.02 (s, 1H), 8.91 (d, J = 7.7 Hz, 1H), 7.73 (d, J = 7.6 Hz, 3H), 6.90-6.84 (m, 1H), 4.43-4.34 (m, 1H), 2.40 (s, 3H), 2.01 (s, 3H), 1.96 (s, 3H).

(Example 5)

  A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C827 (0.500 g, 0.605 mmol), p-toluenesulfonyl chloride (0.058 g, 0.30 mmol), dimethyl sulfoxide (0.236 g, 3.02 mmol) And methyl tert-butyl ether (10 mL) was added. The reaction was stirred at ambient temperature for 24 hours and the resulting brown precipitate was isolated by filtration, washed with methyl tert-butyl ether (2 × 10 mL), then dried under high vacuum to remove C625 as a light brown solid (0.298 g, yield 78.8%).

¹ H NMR (400 MHz, CDCh) δ 16.10 (d, J = 11.3 Hz, 1H), 7.83 (d, J = 111.2 Hz, 1H), 7.08 (s, 1H), 7. 05 (s, 1H), 6.82 (s, 1H), 6.73 (s, 1H), 4.13-4.00 (m, 1H), 4.00-3.78 (m, 3H) , 2.73 (s, 6H), 2.55 (s, 3H), 2.54 (s, 3H), 2.38 (s, 3H), 2.32 (s, 3H), 2.22 ( s, 6H), 1.33 (s, 3H), 1.27 (s, 3H).

(Example 6)

  A magnetic stir bar was attached to a 40 mL scintillation vial, to which C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2 .68 mmol) and toluene (5 mL) were added. The reaction was stirred at ambient temperature for 2 hours and then diluted with diethyl ether (15 mL). The precipitate was isolated by filtration, washed with diethyl ether (20 mL × 2), then hexane (20 mL × 1), then dried under high vacuum to obtain C865 (0.418 g, 90% yield). 0.0%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.72 (d, J = 7.2 Hz, 1H), 7.71 (d, J = 7.7 Hz, 2H), 7.52 (t, J = 7. 3 Hz, 1H), 7.42 (t, J = 7.5 Hz, 2H), 7.33-7.20 (m, 4H), 7.20-7.14 (m, 3H), 7.11 ( d, J = 8.9 Hz, 2H), 7.04 (d, J = 7.0 Hz, 1H), 6.93 (s, 1H), 6.28 (s, 2H), 4.15-4. 03 (m, 1H), 4.03-3.86 (m, 2H), 3.84-3.71 (m, 1H), 2.92-2.85 (m, 2H), 2.84 ( s, 3H), 2.69 (s, 3H), 2.70-2.60 (m, 1H), 2.43 (s, 3H), 2.36 (s, 3H), 2.35 (s , 3H), 2.09 (s, 3H) ), 2.15-2.04 (m, 1H), 2.04-1.90 (m, 2H), 1.78 (s, 3H), 1.82-1.73 (m, 2H).

(Example 7)

  A magnetic stir bar was attached to a 40 mL scintillation vial, to which C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2 .68 mmol) and ethyl acetate (5 mL) were added. The reaction was stirred at ambient temperature for 3 hours and then diluted with diethyl ether (25 mL). The precipitate was isolated by filtration, washed with diethyl ether (2 × 10 mL), then washed with hexane (1 × 20 mL) and then dried under high vacuum to provide C861 (0.386 g, 83% yield). .5%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (d, J = 7.2 Hz, 1H), 7.70 (d, J = 7.7 Hz, 2H), 7.51 (t, J = 7. 2 Hz, 1H), 7.41 (t, J = 7.4 Hz, 2H), 7.33-7.19 (m, 2H), 7.11 (d, J = 8.1 Hz, 2H), 7. 03 (d, J = 7.1 Hz, 1H), 6.92 (s, 1H), 6.27 (s, 2H), 4.11 (dd, J = 14.3, 7.1 Hz, 2H), 4.15-4.02 (m, 1H), 4.03-3.85 (m, 2H), 3.84-3.71 (m, 1H), 2.92-2.79 (m, 2H) ), 2.83 (s, 3H), 2.68 (s, 3H), 2.70-2.59 (m, 1H), 2.42 (s, 3H), 2.35 (s, 3H) , 2.08 (s, 3H), 2.15-2.07 (m, 1H), 2.03 (s, 3H), 2.02-1.90 (m, 2H), 1.77 (s, 3H), 1.82-1. 73 (m, 2H), 1.25 (t, J = 7.1 Hz, 3H).

(Example 8)

  A magnetic stir bar was attached to a 40 mL scintillation vial, to which C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2 .68 mmol) and dichloromethane (4 mL) were added. The reaction was stirred at ambient temperature for 3 hours and then diluted with diethyl ether (30 mL). The precipitate was isolated by filtration, washed with diethyl ether (2 × 10 mL), then washed with hexane (1 × 20 mL), then dried under high vacuum to give C773 (0.345 g, 83% yield). 0.0%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (d, J = 7.1 Hz, 1H), 7.71 (d, J = 7.6 Hz, 2H), 7.52 (t, J = 7. 1 Hz, 1H), 7.42 (t, J = 7.4 Hz, 2H), 7.34-7.19 (m, 2H), 7.11 (d, J = 8.0 Hz, 2H), 7. 03 (d, J = 7.0 Hz, 1H), 6.92 (s, 1H), 6.28 (s, 2H), 4.14-4.03 (m, 1H), 4.03-3. 86 (m, 2H), 3.82-3.72 (m, 1H), 2.83 (s, 3H), 2.91-2.79 (m, 2H), 2.69 (s, 3H) , 2.72-2.60 (m, 1H), 2.42 (s, 3H), 2.36 (s, 3H), 2.18-2.04 (m, 1H), 2.08 (s , 3H). 2.04-1.88 (m, 2H), 1.77 (s, 3H), 1.82-1.73 (m, 2H).

Example 9

  A magnetic stir bar was attached to a 40 mL scintillation vial, to which C848 (0.500 g, 0.589 mmol), p-toluenesulfonyl chloride (0.056 g, 0.30 mmol), tetrahydrothiophene 1-oxide (0.307 g, 2 .94 mmol) and dichloromethane (4 mL) were added. The reaction was stirred at ambient temperature for 1 hour and then diluted with diethyl ether (25 mL). The precipitate was isolated by filtration, washed with diethyl ether (2 × 10 mL), then washed with hexane (1 × 15 mL) and then dried under high vacuum to give C673 (0.248 g, 62% yield). .6%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 16.12 (s, 1H), 7.82 (d, J = 7.7 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H), 7 .23 (t, J = 7.7 Hz, 2H), 7.11 (br s, 2H), 6.93 (s, 1H), 6.29 (s, 1H), 4.11-3.94 ( m, 3H), 3.86-3.76 (m, 1H), 2.72 (s, 3H), 2.69 (s, 3H), 2.64 (s, 3H), 2.62-2 .45 (m, 3H), 2.35 (s, 3H), 2.27-2.17 (m, 1H), 2.15 (s, 3H), 2.07 (s, 3H), 2. 05-1.91 (m, 2H), 1.84-1.68 (m, 2H).

(Example 10)

  A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C827 (0.500 g, 0.605 mmol), p-toluenesulfonyl chloride (0.058 g, 0.30 mmol), tetrahydrothiophene 1-oxide (0.315 g, 3 0.02 mmol) and ethyl acetate (5 mL) were added. The reaction was stirred at ambient temperature for 16 hours. The precipitate was isolated by filtration and recrystallized from dichloromethane / methanol at −30 ° C. The resulting purple crystalline product was isolated by filtration, washed with dichloromethane / methanol (1:10, 5 mL × 2), then dried under high vacuum to provide C651 (0.141 g, 35. Yield). 7%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 16.73 (d, J = 11.3 Hz, 1H), 7.66 (d, J = 11.5 Hz, 1H), 7.09 (s, 1H), 7 .05 (s, 1H), 6.83 (s, 1H), 6.71 (s, 1H), 4.17-4.02 (m, 1H), 4.01-3.84 (m, 3H) ), 3.16-3.06 (m, 1H), 3.02-2.89 (m, 1H), 2.85-2.74 (m, 2H), 2.75 (s, 3H), 2.59 (s, 3H), 2.54 (s, 3H), 2.33 (s, 6H), 2.22 (s, 3H), 2.14 to 2.02 (m, 2H), 1 .99-1.83 (m, 2H), 1.34 (s, 3H), 1.26 (s, 3H).

(Example 11)

A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), dibutyl sulfoxide (0.436 g, 2.69 mmol). And diethyl ether (10 mL) were added. The reaction was stirred at ambient temperature for 12 hours. The precipitate was isolated by filtration, washed with diethyl ether (10 mL x 1), then washed with hexane (20 mL x 1) and then dried under high vacuum to give C831 _m (0.195 g Yield 43.7%).

¹ H NMR (400 MHz, CD ₂ CI ₂ ) δ 8.68-8.60 (m, 1H), 7.77-7.69 (m, 2H), 7.57-7.50 (m, 1H) , 7.44 (t, J = 7.5 Hz, 2H), 7.35-7.28 (m, 2H), 7.15 (s, 1H), 7.13 (dd, J = 5.6, 2.7 Hz, 1H), 7.07 (s, 1H), 6.77 (s, 1H), 6.36 (s, 1H), 6.21 (s, 1H), 4.06-3.95 (M, 1H), 3.94-3.81 (m, 2H), 3.78-3.65 (m, 1H), 2.94 (ddd, J = 14.5, 12.3, 5.. 6 Hz, 1H), 2.77 (s, 3H), 2.70 (s, 3H), 2.64-2.51 (m, 1H), 2.47 (s, 3H), 2.36 (s) , 3H), 1.95 (s, 3H) , 1.73 (s, 3H), 1.71-1.60 (m, 1H), 1.60-1.43 (m, 2H), 1.33-1.19 (m, 2H), 1 .19-1.03 (m, 2H), 0.98-0.91 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H), 0.83-0.70 (m, 1H), 0.48 (t, J = 7.3 Hz, 3H).

(Example 12)

A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C747 (0.590 g, 0.790 mmol), (3,6-dichlorobenzene-1,2-dithiolato) (ethylenediamine) zinc (II) (0.291 g, 0.869 mmol) and tetrahydrofuran (8 mL) were added. The reaction was stirred at ambient temperature for 1 hour and then concentrated to dryness. The resulting residue was extracted with dichloromethane (10 mL), filtered through a celite plug, and then concentrated under high vacuum until about 5 mL. Slow addition of hexane (30 mL) with rapid stirring gives a precipitate which is isolated by filtration, washed with hexane (2 × 10 mL), then dried under high vacuum and C885 _ss (0 604 g, yield 86.4%) was obtained as a dark purple powder.

¹ H NMR (400 MHz, CD ₂ CI ₂ ) δ 7.76 (d, J = 7.3 Hz, 2H), 7.55-7.40 (m, 3H), 7.31 (br s, 1H), 7.20 (br s, 1H), 7.12 (br s, 1H), 7.04 (t, J = 7.3 Hz, 2H), 6.97 (d, J = 6.7 Hz, 1H), 6.84 (br s, 1H), 6.74 (t, J = 7.2 Hz, 1H), 6.31 (d, J = 7.6 Hz, 2H), 6.19 (br s, 1H), 4.03 (brs, 1H), 3.92 (brs, 3H), 2.90 (brs, 3H), 2.64 (brs, 3H), 2.43 (brs, 6H), 2.26 (br s, 6H), 2.18 (br s, 3H), 1.78 (br s, 3H).

(Example 13)

A 40 mL scintillation vial was fitted with a magnetic stir bar, to which C647 (0.300 g, 0.464 mmol), (3,6-dichlorobenzene-1,2-dithiolato) (ethylenediamine) zinc (II) (0.171 g, 0.510 mmol) and tetrahydrofuran (5 mL) were added. The reaction was stirred at ambient temperature for 30 minutes and then concentrated to dryness. The resulting residue was extracted with dichloromethane (20 mL), passed through a 0.2 μm syringe filter, and then concentrated under high vacuum until approximately 4 mL. Diethyl ether (30 mL) was added slowly to give a green microcrystalline precipitate. The product was isolated by filtration, washed with diethyl ether (2 × 5 mL) and dried under high vacuum to give C785 _ss (0.283 g, 77.8% yield).

¹ H NMR (400 MHz, CD ₂ CI ₂ ) δ 14.77 (s, 1H), 7.28 (t, J = 7.3 Hz, 1H), 7.18 (d, J = 8.1 Hz, 1H) 7.10 (d, J = 8.2 Hz, 1H), 7.06 (s, 1H), 6.90-6.81 (m, 4H), 6.47 (d, J = 7.3 Hz, 2H), 6.23 (s, 1H), 4.10-3.90 (m, 4H), 2.71 (s, 3H), 2.68 (s, 3H), 2.66 (s, 3H) ), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s, 3H), 2.21 (s, 3H), 2.02 (s, 3H).

Synthesis of second generation Grubbs ruthenium olefin metathesis catalyst (Example 14)

A 20 mL scintillation vial was fitted with a magnetic stir bar, to which C747 (0.500 g, 0.670 mmol), (PhO) PPh ₂ ([CAS 13360-92-4] 0.196 g, 0.703 mmol) and dichloromethane (5 mL). ) Was added. The reaction was stirred at ambient temperature for 1 hour and then concentrated to 1 mL under high vacuum. Hexane (14 mL) was added and the resulting precipitate was isolated by filtration, washed with hexane (2 × 10 mL) and then dried under high vacuum to give C947 as a reddish brown powder (0.599 g, yield). (Rate 94.5%). This ¹ H NMR data corresponds to the data found in the literature.

(Example 15)

A 20 mL scintillation vial was fitted with a magnetic stir bar, to which C747 (0.500 g, 0.670 mmol), 2-isopropoxy-β-methylstyrene (0.153 g, 0.870 mmol), heptane (5 mL) and methanol ( 1 mL) was added. The reaction was stirred at 60 ° C. for 2 hours and then cooled to ambient temperature. The resulting precipitate was isolated by filtration, washed with methanol (5 mL x 2), and then dried under high vacuum to give C627 as a green solid (0.332 g, 79.1% yield). This ¹ H NMR data corresponds to the data found in the literature.

(Example 16)

A 20 mL scintillation vial was fitted with a magnetic stir bar to which C647 _m (0.400 g, 0.619 mmol), 2-isopropoxy-β-methylstyrene (0.142 g, 0.804 mmol), heptane (5 mL) and methanol. (1 mL) was added. The reaction was stirred at 60 ° C. for 1 hour and then cooled to ambient temperature. The resulting precipitate was isolated by filtration, washed with methanol (2 x 5 mL) and then dried under high vacuum to give C627 as a green solid (0.228 g, 58.9% yield). This ¹ H NMR data corresponds to the data found in the literature.

(Example 17)

To a 20 mL scintillation vial was added C747 (0.300 g, 0.402 mmol), internal olefin [stilbene or β-methylstyrene] (3.6-10 eq) and halogenated solvent (chloroform or dichloromethane, 4 mL). ^The reaction was heated at 40 ° C. or 60 ° C. with stirring until the remaining C747 was less than 5% as determined by ¹ H NMR spectroscopy (2-24 hours). PCy ₃ (0.124 g, 0.442 mmol) was then added and the reaction was stirred for an additional 30 minutes. The yield of C848 was in the range of 50-80% as judged by ¹ H and ³¹ P NMR spectroscopy. This ¹ H NMR data corresponds to the data found in the literature.

Catalytic activity of the olefin metathesis catalyst of the present invention (Example 18)
ROMP reaction of DCPD-HT

The catalytic activity of the complex according to the present invention was evaluated by the ROMP reaction as follows. A 250 mL beaker was charged with 100 g DCPD-HT monomer and 50 ppm CHP. The monomer was equilibrated at the desired temperature in an oil bath (30 ° C. ± 0.5 ° C.). A J-type thermocouple was hung directly in the middle of the monomer. The catalyst for this test was dissolved in a solvent (either toluene or CH ₂ Cl ₂ ) to make a catalyst solution, and this catalyst solution was added at the molar ratio of 45,000: 1 (monomer: catalyst) as described above. In addition to the monomer, a ROMP composition was prepared. Adding the catalyst to the monomer to make a ROMP composition indicated the start of the ROMP reaction and was therefore time point 0. The temperature reading was recorded using a thermocouple. As the ROMP composition transitions from a liquid or gel state to a cured polymer state, a time point has elapsed between time point 0 and the time point at which the propagation interface of the ROMP composition is first visually observed. The exotherm time was determined by measuring the amount of time (ie time difference). The ROMP reaction was stopped 2 hours after the catalyst solution was added to the monomer. The time until heat generation is expressed as follows. Slow over 120 minutes; moderate 30-120 minutes; moderate 1 minute to less than 30 minutes; rapid less than 1 minute and peak exotherm temperature. The results are shown in Table (5).

(Example 19)
RCM of diethyl-2,2-diallylmalonate

CD ₂ Cl ₂ (0.75 mL or 0.775 mL) and catalyst stock in a screw-cap NMR tube fitted with PTFE septum in an argon-filled glove box according to the procedure outlined in Organometallics, 2006, 25, 5740-5745. The solution (0.016M, 50 μL, 0.80 μmol, 1.0 mol% or 0.016 M, 25 μL, 0.80 μmol, 0.5 mol%) was added. The sample was equilibrated at 30 ° C. in a pre-heated NMR probe, and then diethyl 2,2-diallyl malonate (19.3 μL, 19.2 mg, 0.080 mmol, 0.1 M) was added with a syringe. added. Subsequent reactions were monitored for 30 minutes using the Varian array function, and the integral of the methylene proton in the starting material (δ 2.61 (dt)) and the methylene proton in the product (δ 2.98 (s)). By comparing the ratios, the rate of addition to diethylcyclopent-3-ene-1,1-dicarboxylate was determined. FIG. 3 shows the conversion of diethyl 2,2-diallyl malonate to 4,4-bis (ethoxycarbonyl) cyclopentene, and the catalyst is C747, C748, C647, C773, C625, C727 or C705.

(Example 20)
Self-metathesis of cis-5-tetradecene (5C14)

  A magnetic stir bar was attached to a 4 mL scintillation vial in a glove box filled with argon, to which C785ss (0.0046 g, 0.0059 mmol) and tetrahydrofuran (0.5 mL) were added. Cis-5-tetradecene (total 0.150 mL, 0.588 mmol) was then added and the vial was sealed and stirred at 40 ° C. The reaction was sampled at appropriate time intervals and the yield / stereoselectivity was determined by gas chromatography (Method 1) as shown in Table (6).

Claims (20)

Formula (IV)

An olefin metathesis catalyst represented by the structure:
Where
M is a Group 8 transition metal;
L ² is a neutral electron donor ligand;
n is 0 or 1;
m is 0, 1 or 2;
R ^a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ^b is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ^a and R ^b are bonded together to form a 5-membered ring having a sulfoxide group Or form a 6-membered heterocyclic ring;
X ¹ and X ² are independently anionic ligands;
R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are bonded together Form an optionally substituted indenylidene;
X and Y are independently C, CR ^3a or N; only one of X or Y may be C or CR ^3a ;
R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - or ^{- [CR 11 = CR 13]} - is 2 atoms bonded with;
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
“S” and “t” are independently 1 or 2;
R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ⁴ and R ^3a together with the carbon atom to which they are attached are 5-10 members Olefin metathesis catalyst which may form a cyclic cycloalkyl or heterocyclic ring. The olefin metathesis catalyst according to claim 1,
M is Ru;
n is 0;
m is 0;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently halogen;
R ¹ is hydrogen;
R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X and Y are each N;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - is 2 atoms bonded with;
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each hydrogen;
“S” and “t” are each 1;
R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl is selected unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides C ₅ -C ₂₄ aryl substituted with up to 3 substituents,
R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl is selected unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides a C ₅ -C ₂₄ aryl substituted with up to three substituents, the olefin metathesis catalyst. Formula (V)

An olefin metathesis catalyst according to claim 2 represented by the structure:
Where
R ¹ is hydrogen;
R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl;
R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl or phenyl; or R ^a and R ^b are bonded together to form a tetrahydrothiophene oxide having a sulfoxide group. Forming;
X ¹ and X ² are independently Cl, Br, F or I;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl Is;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl. , Olefin metathesis catalyst. An olefin metathesis catalyst according to claim 3,
R ² is phenyl or 2-methyl-1-propenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
An olefin metathesis catalyst wherein X ¹ and X ² are each Cl. An olefin metathesis catalyst according to claim 4,
R ^a is methyl;
R ^b is methyl;
R ³ is 2,4,6-trimethylphenyl;
The olefin metathesis catalyst, wherein R ⁴ is 2,4,6-trimethylphenyl. An olefin metathesis catalyst according to claim 5,
An olefin metathesis catalyst in which R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene. An olefin metathesis catalyst according to claim 3,
R ^a and R ^b are joined together to form a tetrahydrothiophene oxide having a sulfoxide group;
An olefin metathesis catalyst wherein X ¹ and X ² are each Cl. An olefin metathesis catalyst according to claim 7,
R ² is phenyl or 2-methyl-1-propenyl;
R ³ is 2,4,6-trimethylphenyl;
The olefin metathesis catalyst, wherein R ⁴ is 2,4,6-trimethylphenyl. An olefin metathesis catalyst according to claim 7,
R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ³ is 2,4,6-trimethylphenyl;
The olefin metathesis catalyst, wherein R ⁴ is 2,4,6-trimethylphenyl. An olefin metathesis catalyst according to claim 3,

An olefin metathesis catalyst selected from: The olefin metathesis catalyst according to claim 1,
M is Ru;
n is 0;
m is 0;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X ¹ and X ² are independently halogen;
R ¹ is hydrogen;
R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
X is CR ^3a ;
Y is N;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - is 2 atoms bonded with;
“S” and “t” are each 1;
R ³ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl is selected unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides C ₅ -C ₂₄ aryl substituted with up to 3 substituents,
R ⁴ is unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl, or unsubstituted C ₁ -C ₂₀ alkyl, substituted C ₁ -C ₂₀ alkyl, unsubstituted _C 1 _{-C 20} heteroalkyl, substituted _C 1 _{-C 20} heteroalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl, substituted C ₅ -C ₂₄ heteroaryl is selected unsubstituted _C 6 _{-C 24} aralkyl, substituted _C 6 _{-C 24} aralkyl, unsubstituted _C 6 _{-C 24} alkaryl, substituted _C 6 _{-C 24} alkaryl, and halides a C ₅ -C ₂₄ aryl substituted with up to three substituents, the olefin metathesis catalyst. Formula (VII)

An olefin metathesis catalyst according to claim 11 represented by the structure:
Where
R ¹ is hydrogen;
R ² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene;
R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are bonded together to form a 5-membered sulfoxide group Forming a ring or a 6-membered heterocyclic ring;
X ¹ and X ² are independently Cl, Br, I or F;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2- iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl or 2-methyl-phenyl;
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C ₁ -C ₁₂ alkyl, substituted C ₁ -C ₁₂ alkyl, unsubstituted C ₁ -C ₁₂ heteroalkyl, substituted C _1- C ₁₂ heteroalkyl, unsubstituted _C 4 _{-C 12} cycloalkyl, substituted _C 4 _{-C 12} cycloalkyl, unsubstituted _C 5 _{-C 24} aryl, substituted _C 5 _{-C 24} aryl, unsubstituted _C 5 _{-C 24} heteroaryl , Substituted C ₅ -C ₂₄ heteroaryl, unsubstituted C ₆ -C ₂₄ aralkyl, substituted C ₆ -C ₂₄ aralkyl, unsubstituted C ₆ -C ₂₄ heteroaralkyl or substituted C ₆ -C ₂₄ heteroaralkyl;
R ^3a is methyl, ethyl, n-propyl or phenyl;
R ⁴ is methyl, ethyl, n-propyl or phenyl; or R ⁴ and R ^3a together with the carbon atom to which they are attached form a 5-10 membered cycloalkyl or heterocyclic ring. Olefin metathesis catalyst. The olefin metathesis catalyst according to claim 1,
M is Ru;
n is 0;
m is 0;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
X and Y are each N;
Q has the structure _{^{- [CR 11 R 12] s}} - [CR 13 R 14] t - is 2 atoms bonded with;
“S” and “t” are each 1;
R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene And
portion

Is;
X ³ and X ⁴ are each S;
R ^x , R ^y , R ^w and R ^z are independently C ₁ -C ₆ alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; or R ^x and R ^y are bonded together, Forming an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted Olefin metathesis forming bicyclic or polycyclic aryl; or R ^y and R ^w are joined together to form unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl catalyst. Formula (VIII)

An olefin metathesis catalyst according to claim 13 represented by the structure:
Where
R ^a is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;
R ^b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R ^a and R ^b are bonded together to form a 5-membered sulfoxide group Forming a ring or a 6-membered heterocyclic ring;
R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2- iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butyl Phenyl, 2,4-dimethylphenyl or 2-methyl-phenyl;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso- Propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl;
R ¹ is hydrogen and R ² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R ¹ and R ² are joined together to form an optionally substituted indenylidene And
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently C ₁ -C ₆ alkyl or hydrogen;
R ^x , R ^y , R ^w and R ^z are independently C ₁ -C ₆ alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; or R ^x and R ^y are bonded together, Forming an unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl; or R ^w and R ^z joined together to form an unsubstituted bicyclic or polycyclic aryl or substituted Olefin metathesis forming bicyclic or polycyclic aryl; or R ^y and R ^w are joined together to form unsubstituted bicyclic or polycyclic aryl or substituted bicyclic or polycyclic aryl catalyst. Formula (B)

A process for synthesizing an olefin metathesis catalyst represented by
Said method comprises formula (V)

Contacting an olefin metathesis catalyst represented by the structure of: and a PR ^d R ^e OR ^f ligand in an inert solvent at room temperature, wherein
R ¹ is hydrogen;
R ² is phenyl or 2-methyl-1-propenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ³ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl or 2-iso-propyl-6-methylphenyl;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl or 2-iso-propyl-6-methylphenyl;
X ¹ and X ² are each Cl;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
R ^d is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C _{3 to} C ₈ cycloalkyl;
R ^e is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C _{3 to} C ₈ cycloalkyl;
R ^f is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₆ -C ₁₀ aryl, unsubstituted C ₆ -C ₁₀ aryl, substituted C ₃ -C ₈ cycloalkyl or unsubstituted C ₃ -C ₈ cycloalkyl, method. 16. A method according to claim 15, comprising
R ¹ is hydrogen and R ² is phenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ³ is 2,4,6-trimethylphenyl;
R ⁴ is 2,4,6-trimethylphenyl;
R ^a is methyl;
R ^b is methyl;
R ^d is phenyl;
R ^e is phenyl;
A method wherein R ^f is phenyl, methyl, p- (OMe) phenyl, iso-propyl or ethyl. The method according to claim 16, comprising:
R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
The method wherein R ^f is phenyl. Formula (D)

A process for synthesizing an olefin metathesis catalyst represented by
Said method comprises formula (V)

An olefin metathesis catalyst represented by the structure of:
formula

Contacting with a ligand of in an inert solvent, wherein
R ¹ is hydrogen;
R ² is phenyl or 2-methyl-1-propenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ³ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl or 2-iso-propyl-6-methylphenyl;
R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl or 2-iso-propyl-6-methylphenyl;
X ¹ and X ² are each Cl;
R ^a is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl;
R ^b is unsubstituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₁₀ cycloalkyl, substituted C ₃ -C ₁₀ cycloalkyl, unsubstituted C ₅ -C ₂₄ aryl or substituted C ₅ -C ₂₄ aryl; or R ^a and R ^b are joined together to form a 5- or 6-membered heterocyclic ring having a sulfoxide group;
R ^k is hydrogen, halogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR ^s ₂ , —NHC (O) CF ₃ , —NHC (O) C ₆ F ₅ , —NHC (O) OtBu Hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ¹ is hydrogen, halogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR ^s ₂ , —NHC (O) CF ₃ , —NHC (O) C ₆ F ₅ , —NHC (O) OtBu Hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ^m is hydrogen, _{^{halogen, -NO 2, -CN, -CF 3}} , -SO 2 NR s 2, -NHC (O) CF 3, -NHC (O) C 6 F 5, -NHC (O) OtBu Hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ⁿ is hydrogen, halogen, —NO ₂ , —CN, —CF ₃ , —SO ₂ NR ^s ₂ , —NHC (O) CF ₃ , —NHC (O) C ₆ F ₅ , —NHC (O) OtBu Hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
R ^s is hydrogen or C ₁ -C ₆ alkyl;
The method wherein R ^q is C ₁ -C ₁₀ alkyl. The method according to claim 18, comprising:
R ¹ is hydrogen and R ² is phenyl; or R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene;
R ^a is methyl;
R ^b is methyl;
R ³ is 2,4,6-trimethylphenyl;
R ⁴ is 2,4,6-trimethylphenyl;
R ^k is hydrogen;
R ¹ is hydrogen;
R ^m is hydrogen;
R ⁿ is hydrogen;
The method wherein R ^q is iso-propyl. 20. The method according to claim 19, comprising
A method wherein R ¹ and R ² are joined together to form 3-phenylindene-1-ylidene.

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